Paper: Orpiment Under Compression: Metavalent Bonding at High Pressure

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Orpiment under compression: metavalent

bonding at high pressure†
Published on 08 January 2020. Downloaded by Universite De Liege on 11/3/2020 8:28:29 AM.
Cite this: Phys. Chem. Chem. Phys.,

2020, 22, 3352
Vanesa Paula Cuenca-Gotor, a Juan Ángel Sans, *a Oscar Gomis, b
Andres Mujica,c Silvana Radescu,c Alfonso Muñoz, c Plácida Rodrı́guez-
Hernández, c Estelina Lora da Silva, a Catalin Popescu, d Jordi Ibañez, e
Rosario Vilaplanab and Francisco Javier Manjón *a
We report a joint experimental and theoretical study of the structural, vibrational, and electronic
properties of layered monoclinic arsenic sulfide crystals (a-As2S3), aka mineral orpiment, under
compression. X-ray diffraction and Raman scattering measurements performed on orpiment samples at
high pressure and combined with ab initio calculations have allowed us to determine the equation of
state and the tentative assignment of the symmetry of many Raman-active modes of orpiment. From
our results, we conclude that no first-order phase transition occurs up to 25 GPa at room temperature;
however, compression leads to an isostructural phase transition above 20 GPa. In fact, the As
coordination increases from threefold at room pressure to more than fivefold above 20 GPa. This
increase in coordination can be understood as the transformation from a solid with covalent bonding to
a solid with metavalent bonding at high pressure, which results in a progressive decrease of the
electronic and optical bandgap, an increase of the dielectric tensor components and Born effective
charges, and a considerable softening of many high-frequency optical modes with increasing pressure.
Received 21st November 2019, Moreover, we propose that the formation of metavalent bonding at high pressures may also explain the
Accepted 8th January 2020 behavior of other group-15 sesquichalcogenides under compression. In fact, our results suggest that
DOI: 10.1039/c9cp06298j group-15 sesquichalcogenides either show metavalent bonding at room pressure or undergo a
transition from p-type covalent bonding at room pressure towards metavalent bonding at high pressure,
rsc.li/pccp as a precursor towards metallic bonding at very high pressure.
A Introduction a-As2S3, canary yellow or King’s yellow pigment was obtained from
molten orpiment and has been extensively used in papyrus and
Arsenic sulfide (As2S3) and in particular the monoclinic polymorph objects of ancient Egypt that date back to 3.1 millennia BC.3–5
(a-As2S3), aka mineral orpiment, is one of the ores of As together Additionally, As2S3 crystals and glasses have been used as drugs to
with minerals realgar (a-As4S4) and arsenopyrite (FeAsS).1 In treat different illnesses, such as prophylactic diseases, asthma,
particular, orpiment and realgar have been known since ancient tuberculosis or diabetes, and were also prescribed as antiseptics
times, with realgar being used as an orange-red pigment and and sedatives by Aristotle and Hippocrates (IV century BC).
orpiment as a gold-like pigment, hence its mineral name orpiment Moreover, orpiment has been used since ancient times in
(Aurum pigmentum in Latin).2 Due to the high chemical stability of traditional Chinese medicine6 until nowadays, when arsenic
sesquisulfide has proved to exhibit positive effects in cancer
therapy.7 Finally, it must be stressed that in the last decades
a
Instituto de Diseño para la Fabricación y Producción Automatizada, MALTA arsenic sulfides have been investigated for different applications
Consolider Team, Universitat Politècnica de València, 46022 Valencia, Spain.
in photonics and non-linear optics since they possess high values
E-mail: juasant2@upv.es, fjmanjon@fis.upv.es
b
Centro de Tecnologı́as Fı́sicas, MALTA Consolider Team, Universitat Politècnica de
of the refractive index, high IR transparency, high optical
València, 46022 Valencia, Spain non-linearity, stability to crystallization, the possibility to be
c
Departamento de Fı́sica, Instituto de Materiales y Nanotecnologı́a, MALTA modified by femtosecond laser irradiation, and an inertness to
Consolider Team, Universidad de La Laguna, 38200 San Cristóbal de La Laguna, the environment.8,9
Spain
d
As2S3 usually crystallizes in the monoclinic a polymorph
ALBA-CELLS, MALTA Consolider Team, 08290 Cerdanyola, Barcelona, Spain
e
Institute of Earth Sciences Jaume Almera, MALTA Consolider Team, CSIC,
[space group (SG) P21/n or P21/c, No. 14];10,11 although a triclinic
08028 Barcelona, Spain dimorph of orpiment called anorpiment [SG P1% , No. 2] was
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c9cp06298j recently discovered and approved as a new mineral by the
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Fig. 1 a-As2S3 structure at room pressure. Big yellow and small purple spheres correspond to S and As atoms, respectively. (a) 3D structure. All solid lines
correspond to bonds of similar length (B2.3 Å) and dashed lines correspond to longer As–S distances (43.0 Å). (b) Structure of the layer in the ac plane
showing the heart-shaped rings. The upper part shows the AsS3 pyramids due to the short bonds that result in the threefold coordination of As and
twofold coordination of S at room pressure. Inside the cell edges we show the long intralayer bonds that would contribute to fivefold coordination of As
above 25 GPa. (c) Structure viewed as AsS spiral chains (in the As1–S1–As2–S2 sequence) joined by inter-chain S3 atoms. Only short bonds are displayed.
Solid (dashed) lines correspond to intra (inter)-chain bonds. (d) Projection of the a-As2S3 structure onto the bc plane. (e) 3D structure of As2S3 at 30 GPa,
showing polyhedral units with fivefold coordination of As1 and As2 atoms (up and middle) and with 5 + 2 coordination for As1 atoms (down).
International Mineralogical Association.12 The crystalline structure Besides, HP-XAS measurements suggested some structural
of the monoclinic a phase (see Fig. 1) is composed of corrugated or changes above 10 GPa and an increase in the As coordination
zigzag layers piled up mainly along the b axis (see Fig. 1(a)), which above 30 GPa. On the other hand, recent electrical measurements
are linked by weak van der Waals (vdW) forces.13 and calculations suggest an isostructural phase transition (IPT)
The properties of arsenic sulfides have been extensively around 25 GPa.33
studied, mainly for melts and glasses, because As2S3 ranks first To verify these hypotheses, it would be desirable to perform
among chalcogenides from the viewpoint of the production of HP X-ray diffraction (XRD) measurements on a-As2S3 at room
amorphous and glass-like industrial materials. However, many temperature in order to obtain the equation of state of orpiment
properties of their crystalline phases, orpiment and anorpiment, and explore the origin of the changes proposed in the literature.
are not yet well known, likely due to the complex monoclinic and Such measurements will allow us to investigate the possible
triclinic crystalline structures of these compounds. For instance, appearance of HP phases and their relationship mainly with
a definitive symmetry assignment of the vibrational modes of those of other sesquioxides and sesquichalcogenides. On the
orpiment is still under debate14 despite a number of papers other hand, it will be important to perform new HP-RS measure-
reporting Raman scattering (RS) measurements, as well as ments in order to correlate the structural and vibrational changes
infrared (IR) measurements, since the advent of laser-based in orpiment and to aid in the assignment of the symmetries and
Raman spectroscopy.14–29 the origin of the different vibrational modes with the help of
In this context, pressure is a valuable tool to study the ab initio calculations. All these measurements and calculations
properties of materials and several high-pressure (HP) studies would allow us to understand the behavior of orpiment under
have been performed on glassy As2S3 and a-As2S3 in order to compression.
help us to understand their properties. In particular, results For all the mentioned reasons, we report in this work a joint
obtained from HP optical absorption, HP X-ray absorption experimental and theoretical study of the structural, vibrational, and
spectroscopy (XAS), HP-RS measurements, HP electrical measure- electronic properties of a-As2S3 under compression at room tem-
ments and from a few ab initio calculations have been reported for perature by means of powder HP-XRD and HP-RS measurements on
a-As2S3.23,26,27,30–35 Moreover, a HP and high-temperature (HT) orpiment, where our experimental results are complemented with
polymorph of orpiment (a-As2S3), whose structure has not been theoretical ab initio total-energy, lattice-dynamics and electronic
resolved yet, has been found.34 This is not surprising because little band structure calculations.
is also known about the structure of orpiment and its behavior Our structural results show continuous compression of
under compression. It is only known that the remarkable orpiment up to 25 GPa with a large decrease of the interlayer
high packing of layers in orpiment is responsible for its high distance, coherent with the loss of the vdW character of the
stability under pressure as suggested by previous experiments. dominating forces in this region. A progressive increase of the
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As coordination with compression, changing from threefold AsS chains extended along the a-axis and held together by inter-
coordination at 0 GPa to more than fivefold coordination above chain S atoms, which allow the link between the chains along the
20 GPa, occurs as a consequence of a pressure-induced IPT c-axis (see Fig. 1(c)). On the other hand, zigzag layers can also be
around 20 GPa. Moreover, our experimental and theoretical seen as a W-shape formation of molecules (S1–As2–S3–As1–S2)
results show a strong elastic anisotropy of orpiment layers where each molecule is linked with four adjacent inverted
between 0 and 23 GPa, which confirms recent results36 and W-shape molecules, mostly along the c-axis due to covalent
opens the door to the use of membranes of this 2D material in bonding (see Fig. 1(d)).
flexible and stretchable devices.37,38 At room conditions, each As1 and As2 atom is linked by
Additionally, our vibrational results show a closing of the covalent bonds to one S1, one S2 and one S3 atom at distances
phonon gap with increasing pressure up to 16 GPa due to the around 2.3 Å, leading to As threefold-coordination (see the
large number of phonons with negative pressure coefficients pyramids in Fig. 1(a)). Additionally, each As1 and As2 atom has
(soft modes) at relatively low pressures. Our theoretical calculations two farther S neighbors in the same layer at distances above
have allowed us to provide a tentative symmetry assignment of the 3.0 Å (see the dashed lines inside the layers in Fig. 1(a) and (b))
Raman-active modes in orpiment and explain their behavior under and another two S neighbors in an adjacent layer at distances
compression, which can help in identifying orpiment in ancient above 3.5 Å (see the dashed lines between the layers in the top
pigments in a non-destructive way.39 part of Fig. 1(a) and (d)). In the following section, we will discuss
Our electronic band structure calculations suggest that there the importance of these long As–S intra- and interlayer distances
is a progressive closing of the bandgap of a-As2S3 with increasing (above 3 Å at room pressure) in orpiment at high pressure.
pressure leading from a trivial semiconductor to a trivial metal According to the difference of the As–S distances, we can
well above 60 GPa, which is in very good agreement with previous consider orpiment as an arrangement of AsS3 pyramids forming
optical absorption measurements26,27,31 and suggests a possible AsS3E tetrahedral units, where E refers to the lone electron pair
phase transition above 42 GPa due to the recently observed (LEP) of the As atoms. Therefore, each layer can be described
metallization of orpiment.33 alternatively by an arrangement of two tetrahedral AsS3E units,
Finally, we show that all the changes observed in orpiment i.e. those formed by the two inequivalent As atoms, each
under compression, such as: the strong decrease of the band- surrounded by three S atoms and the corresponding cation
gap; the softening of many optical vibrational modes; the LEP that points towards the interlayer space. The strong As LEP
evolution of the electron localization function (ELF) along the distorts the electronic distribution and the geometry of the
As–S bonds; and the strong increase of the dielectric tensor polyhedral units leading to the layered structure of orpiment.
components and Born effective charges, can be explained in the The layered structure of orpiment bears similarities with the
framework of the formation of metavalent bonding at HP, as chain-like structure of the valentinite mineral (b-Sb2O3), where
recently proposed for other chalcogenides.40–45 In summary, we the W-shape molecules (linked through a helical form) lead to
show in the present paper that orpiment under compression is the formation of an acicular or quasimolecular crystal.46 On the
an example, together with GeSe,43 of a compound that develops other hand, the layered structure of orpiment is isostructural to
a pressure-induced transition from covalent to metavalent that of a-As2Se347 and belongs to the same space group as the
bonding without the need to undergo a first-order structural claudetite mineral (m-As2O3); however, claudetite is not isostructural
phase transition. This feature contrasts with Se and Te, which to orpiment, because the layered structure of the former is due to
undergo this change of bonding character after being the the arrangement of AsO3 molecules in a buckled structure48 as in
subject of a first-order phase transition. Moreover, we propose black phosphorous.49 The layered structure of orpiment also bears
that the formation of metavalent bonding may explain the some resemblance to the zigzag layered structure recently described
behavior under compression of other group-15 chalcogenides, for Sb2S3, Sb2Se3, and Bi2S3,50–52 crystallizing in the orthorhombic
so our results pave the way for extending the study of the Pnma structure, and to that of a-As2Te3, crystallizing in the mono-
transformation from covalent to metavalent bonding to other clinic C2/m phase.53 In these former group-15 A2X3 sesquichalco-
group-15 chalcogenides and related compounds. genides, the layers are clearly composed of spiral chains held
together through long and weak A–X bonds, whereas in As2S3 the
chains are connected through short and strong A–X bonds. Another
B Results difference found between these systems is regarding the cation
coordination in the different structures at room pressure. In a-As2S3,
B.1 Structural and vibrational characterization of a-As2S3 at the two inequivalent As atoms are threefold-coordinated; in Sb2S3,
room conditions Bi2S3 and Sb2Se3, there is an average fourfold coordination because
As already commented on, a-As2S3, with the monoclinic P21/c one cation has threefold coordination and the other has fivefold
space group at room conditions, is a layered material with coordination; and in a-As2Te3, the As atoms have coordination
corrugated (or zigzag) layers extended along the ac-plane that are between five and six. This means that the larger cation or the
linked by vdW interlayer interactions along the b-axis (Fig. 1(a)). larger anion favors an increase of cation coordination probably
Each corrugated layer is formed by heart-shaped six-member due to the smaller cation LEP effect.54
rings of corner-sharing AsS3 pyramids (Fig. 1(b)) Traditionally, The experimental XRD pattern of our sample at room
the zigzag layers have been understood as being formed by spiral conditions (see Fig. 2(a)) shows that the sample corresponds
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The theoretical atomic parameters of the five inequivalent

atomic sites (three S and two As atoms) of a-As2S3 are also given
in Table S1 in the ESI,† for comparison with the experimental
and theoretical values.
As regards the vibrational properties of a-As2S3, group theory
predicts sixty vibrational modes at the Brillouin zone (BZ)
center with the following mechanical representation:56
G60 = 15Ag (R) + 13Bu (IR) + 15Bg (R) + 14Au (IR) + 1Au + 2Bu
(1)
where g (gerade) modes are Raman-active (R) and u (ungerade)

modes are infrared-active (IR), except one Au and two Bu modes
that are acoustic modes. Therefore, a-As2S3 has 30 Raman-
active modes and 27 IR-active modes.
Fig. 2(b) shows the unpolarized RS spectrum of orpiment at
room conditions together with the theoretically-predicted Raman-
active mode frequencies at room pressure. The values of the
experimental and theoretical frequencies of the Raman-active
modes of a-As2S3 at room pressure are summarized in Table 2.
The RS spectrum of orpiment at room pressure clearly shows 19
out of the 30 theoretically-predicted Raman-active modes and
quite good agreement between our experimental and theoretical
frequencies (including vdW interactions). The spectrum is
similar to those previously reported, with a doublet between
60 and 70 cm1, a phonon gap between 200 and 290 cm1 and a
triplet around 360 cm1.14–29,33 Unfortunately, we have not been
able to observe modes below 40 cm1 due to the limit imposed
by the edge filter of our spectrometer.
Fig. 2 Structural and vibrational characterization of a-As2S3 at room
The vibrational spectrum of orpiment at room pressure is
conditions: (a) powder XRD pattern (circles). Le Bail analysis (black solid separated between a low-frequency region (below 200 cm1)
line) and residuals (red solid line) are also plotted. (b) RS spectrum. The and a high-frequency region (above 260 cm1) with a phonon
bottom marks indicate the theoretical Raman-active mode frequencies gap between both. Some Raman features are observed inside
from calculations including vdW interactions. The asterisks indicate 2nd
the phonon gap of a-As2S3, which are assumed to be second-
order Raman features.
order modes, so they will not be further commented on in this
work. Among the measured RS modes, the more intense modes
to the a-phase without the presence of additional phases or are those of the high-frequency region between 350 and
impurities, within the detection limits of the technique. The 360 cm1. Due to the large number of Raman-active modes
pattern was fitted to a monoclinic structure (P21/c space group), located within a small frequency region of the RS spectrum at
with small residuals and a correlation factor Rwp of 10%, room pressure and the broadening of experimental peaks, it is
yielding the following lattice parameters: a = 4.2626(5) Å, almost impossible to identify the modes by solely using the RS
b = 9.6056(7) Å, c = 12.1836(12) Å and b = 110.054(7)1 with spectrum at room pressure and its comparison with lattice-
V0 = 468.61(5) Å3. In Table 1 we can observe that these values are dynamics ab initio calculations. Therefore, a tentative assignment
in good agreement with previously reported experimental of experimental peaks will be performed in a forthcoming section
values,10,11,13 with our theoretically calculated lattice parameters taking into account the HP dependence of the experimental and
and with other previously published theoretical data.33,55 theoretical Raman-active mode frequencies.
Table 1 Experimental and theoretical (with vdW) lattice parameters corresponding to the P21/c phase of a-As2S3 at ambient conditions. Experimental
and theoretical values from ref. 10, 11, 33 and 72 are given for comparison. All data have been expressed in the standard P21/c setting for comparison
Lattice Experimental Theoretical Experimental Experimental Theoretical Theoretical

parameters (this work) (this work) (ref. 11) (ref. 10) (ref. 33) (ref. 72)
a (Å) 4.2626(5) 4.2608 4.256(2) 4.22(5) 4.22 4.22
b (Å) 9.6056(7) 9.6289 9.577(5) 9.57(2) 9.65 9.57
c (Å) 12.1836(12) 12.3084 12.191 (5) 12.18(4) 12.27 12.1839
b (1) 110.054(7) 109.84 109.75(8) 109.8(5) 109.59 109.85
V0 (Å3) 468.61(5) 475.00 467.68 462.8 471.2 462.80
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Table 2 Theoretical (with vdW interactions) and experimental Raman-active mode frequencies and their respective pressure coefficients for a-As2S3 at
room temperature, as fitted with equation o(P) = o0 + aP. Experimental values from ref. 23, 25 and 33 have been added for comparison
Theoretical Experimental
1 1 1
Mode a
o0 (cm ) a
a (cm GPa ) o0a (cm1) aa (cm1 GPa1) o0 (cm1) a (cm1 GPa1)
A1g 27 (1) 5.1 (3) 26 (1) 6.32 (37) 25b, 26c 9.0b
A2g 38 (1) 4.5 (2) 37 (1) 4.9 (3) 36b, 37c 7.2b
A3g 59 (1) 4.1 (2) 62 (1) 3.7 (1)
B1g 62 (1) 1.6 (2) 62b,c 5.0b
B2g 68 (1) 10.3 (4) 69 (3) 10.5 (8) 69b, 70c 11.0b
A4g 70 (1) 5.9 (3) 70 (3) 8.1 (3)
B3g 94 (2) 3.1 (1) 103 (2) 2.9 (1)

B4g 103 (2) 2.1 (5) 106 (2) 2.8 (1) 107b, 106c 4.9b
A5g 124 (2) 7.7 (7) 138 (5) 5.1 (4) 136b, 137c, 135d 7.3b, 0.42d
B5g 134 (2) 0.7 (2) 120 (1) 2.9 (5)
B6g 135 (2) 3.6 (1) 144 (1) 3.9 (2) 145c
B7g 152 (3) 3.7 (2)
A6g 153 (3) 4.6 (7) 155 (2) 0.3 (3) 158c
A7g 155 (3) 5.5 (3) 156 (2) 6.9 (4) 154b,c, 153d 8.5b, 0.24d
B8g 174 (3) 2.5 (2) 179 (2) 2.2 (1) 180c, 177d 2.22d
A8g 176 (3) 1.2 (1) 185 (2) 2.3 (1)
B9g 181 (3) 3.3 (2) 188 (2) 4.6 (9) 188c
A9g 196 (3) 1.3 (1) 202 (1) 2.5 (2) 202b, 204c, 201d 3.2b
A10
g 270 (4) 3.1 (2) 291 (1) 2.6 (3) 292b, 293c, 290d 3.8b, 0.89d
B10
g 290 (4) 0.3 (1) 306 (2) 0.5 (1) 307c, 308d 0.2d
A11
g 291 (4) 1.3 (1) 310 (2) 1.4 (1) 310b, 312c 1.0b
B11
g 305 (4) 2.7 (1) 325 (2) 3.5 (4) 326b,c 4.6b
B12
g 329 (5) 3.7 (1) 343c
A12
g 341 (5) 1.0 (5) 356 (4) 0.7 (6)e 357b, 360c 0.96b
A13
g 343 (5) 3.4 (3) 354 (4) 1.8 (4)e 356c
B13
g 345 (5) 3.1 (1)
A14
g 346 (5) 0.5 (1) 353 (4) 4.1 (6)e 354c, 353d 0.19d
B14
g 350 (5) 3.1 (4) 369 (2) 2.2 (3) 370c
A15
g 369 (5) 2.4 (1) 383 (2) 2.2 (2) 383b, 384c, 380d 1.7b, 0.47d
B15
g 385 (5) 0.9 (2) 400 (2) 0.7 (3) 401c
a b
This work. Ref. 23. c Ref. 25. d
Ref. 33. e The pressure coefficient of these modes has been measured above 2 GPa.
The atomic vibrations of several characteristic Raman- and As regards other vibrational modes of orpiment, those of the
IR-active modes of a-As2S3 have been visualized with the aid of high-frequency region mainly correspond to As–S stretching
the Jmol Interface for Crystallographic and Electronic Properties modes located between 350 and 400 cm1 and to a mixture of
(J-ICE) interface57 (see Fig. S1–S14 in the ESI†) and discussed in As–S stretching and bending modes between 260 and 350 cm1.
the ESI.† An interesting feature is that many vibrations evidence On the other hand, the modes located below 200 cm1 correspond
that atoms of the same chain (As1, S1, As2, and S2) vibrate to pure As–S bending modes, with those below 100 cm1 being
in-phase or out-of-phase, whereas the S3 atoms interconnecting mainly related to rotations and translations of the spiral chains.
the chains vibrate in a quite different fashion than the other This result shows that spiral chains in orpiment are clearly defined
four inequivalent atoms. This observation clearly evidences the rigid units. This distribution of modes agrees well with previous
chain-like nature of the layers of orpiment in good agreement works that assigned the As–S bending modes and As–S stretching
with a previous vibrational study.24 modes near 200 and 400 cm1, respectively.18,58 In fact, the modes
As a layered material, some of the most important vibrational close to 380 and 350 cm1 can be assigned to the antisymmetric
modes of a-As2S3 are the rigid layer modes. Our calculations and symmetric As–S stretching vibrations inside the spiral chains,
confirm that the two lowest-frequency modes located at 27 and respectively, in good agreement with previous estimations.28
38 cm1, and attributed to the A1g and A2g modes, correspond to
the rigid shear layer modes of orpiment (Fig. S1 in the ESI†). B.2 Structural characterization of a-As2S3 at HP
Moreover, our calculations show that the compressional or Fig. 3 shows powder HP-XRD patterns of orpiment at selected
longitudinal rigid layer mode is the B1g mode theoretically pre- pressures up to 26.6 GPa. The XRD patterns were analyzed
dicted at 62 cm1 (Fig. S2 in the ESI†). This frequency value is in by means of Le Bail fits to the monoclinic P21/c structure,
good agreement with previous estimations of the compressional which is stable up to the maximum achievable pressure. Le Bail
mode.22 At room pressure, we have observed that this mode is analysis of this material allowed the possibility of obtaining the
within a region where it is overlapped with inter-chain vibrational structural parameters of a-As2S3 at different pressures (see Fig. 4).
modes (see comments in the ESI†), as previously suggested.24 A progressive increase of the Bragg peak width was observed and
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Fig. 4 (a) Experimental (symbols) and theoretical (solid lines) pressure

dependence of the unit-cell volume in a-As2S3. Black (blue) solid lines
represent data from calculations including (not including) vdW interactions.
The dashed lines correspond to experimental data fit with a 3rd order
BM-EoS. (b) Experimental (symbols) and theoretical (solid lines) pressure
dependence of the lattice parameters and monoclinic b angle (inset) in
a-As2S3. All calculations include vdW interactions. Anorpiment EoS curve
theoretically simulated is included for the sake of comparison (red solid line).
and the order of the BM-EoS was determined by the monoto-

nously positive slope of the Eulerian strain vs. normalized
pressure plot of the theoretically simulated data. This plot
agrees with highly compressible non-covalent compounds with
large cation LEP activity, as has been observed for structurally-
related sesquichalcogenides, such as Sb2S3, Sb2Se3, Bi2S3 and
a-As2Te3, characterized by bulk modulus pressure derivatives
Fig. 3 Powder HP-XRD patterns of a-As2S3 at selected pressures up to
26.6 GPa. The patterns are shifted vertically for comparison.
larger than 4.52,53
Our experimental bulk modulus and pressure derivative
under hydrostatic conditions for orpiment can be compared
explained in the framework of a progressive loss of the hydro- to our theoretical data with and without vdW interactions. As
static conditions. The layered nature of this material prevents expected in the description of Fig. 4(a), the theoretical bulk
obtaining fine powder for this measurement, which led to the modulus is closer to the experimental one when the calculations
lack of Rietveld refinement of our XRD patterns. include vdW interactions (B0 = 12.7(5) GPa) than when the
A monotonous decrease of the unit-cell volume of orpiment calculations do not include them (B0 = 16.1(12) GPa). Nevertheless,
up to 26.6 GPa is observed in Fig. 4(a), where experimental the theoretical pressure derivative of the bulk modulus at zero
volume data at several pressures have been compared with pressure is considerably smaller than the experimental value
density functional theory (DFT) calculations, both including (B0 0 = 8.9(5)) in the case of the simulations with vdW inter-
and without including vdW interactions. At low pressures, the actions (B0 0 = 7.0(14)) than in the simulations without vdW
pressure dependence of the experimental volume agrees quite interactions (B0 0 = 7.9(6)). A comparison of these results with
well with the theoretical simulation when vdW interactions are similar compounds, such as the claudetite polymorph of As2O3
included. However, the experimental data above 10 GPa show a or a-As2Te3, indicates that orpiment presents a similar value of
poorer agreement with these calculations and much better the bulk modulus to the former (B0 = 15.5(4) GPa),60 but a much
agreement with calculations that do not include vdW inter- smaller value of the bulk modulus than the latter (B0 = 24(3) GPa).53
actions. The above experimental result indicates that orpiment This result is consistent with the higher LEP activity of As atoms in
is more incompressible above 10 GPa, likely due to the loss oxides and sulfides than in selenides and tellurides.54
of quasi-hydrostatic conditions of the pressure-transmitting The pressure dependence of the experimental and theore-
medium above this pressure. tical lattice parameters of a-As2S3 up to 26.6 GPa also shows a
The fit of pressure vs. experimental volume up to 10 GPa monotonous and smooth decrease (see Fig. 4(b)). The good
through a third-order Birch–Murnaghan Equation of State agreement of the theoretical behavior of the volume and lattice
(BM-EoS)59 according to the trend shown by its F–f plot parameters with our experimental data at room temperature
(Fig. S15 in the ESI†) yields a zero-pressure volume, bulk modulus allows us to conclude that no first-order phase transition occurs
and pressure derivative of the bulk modulus of: V0 = 468.61(5) Å3, throughout the whole range of studied pressures. In particular,
B0 = 13.3(5) GPa and B0 0 = 8.9(5), respectively. The volume at zero the lack of a jump in the pressure dependence of our lattice
pressure, V0, was fixed to the value measured outside the DAC parameters and unit-cell volume in the region close to 10 GPa
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lead us to discard the presence of a structural phase transition spiral layers along the a-axis. Moreover, the compressibility of the
in this pressure range, as was previously suggested.30 Therefore, a-axis (b11) is much larger than that of the c-axis (b33). This high
our results are in good agreement with recently published intralayer elastic/mechanic anisotropy is consistent with that
theoretical data.33 recently found in As2S3 nanolayers, which is similar to that of black
The analysis of the axial compressibility in monoclinic phosphorous,36 and certifies that orpiment layers can be
structures requires a more complex analysis than for more sym- potentially used in flexible, stretchable, orientation-dependent
metric phases because the b-angle is not 901, so the directions of and frequency tunable electronic, optoelectronic and opto-
maximum and minimum compressibility of the compound are mechanic devices.37,38
usually not along any of the three crystallographic axes. Therefore, The compressibility trend among the different crystallo-
we have analyzed the compressibility of the material by calculating graphic directions remains constant (b11 4 b22 4 b33) up to
and diagonalizing the experimental and theoretical isothermal 23 GPa. In this pressure range, all compressibilities are positive,
compressibility tensor bij at different pressures (details are given thus indicating a monotonous compression of the structure
in the ESI†). This tensor is a symmetric second rank tensor that along the three main crystallographic axes up to 23 GPa. This
relates the state of strain of a crystal to the pressure change that result is somewhat in disagreement with previous estimates by
induced it61 and it has been obtained with the finite Eulerian Besson et al.,26 who found positive and negative values for the
approximation as implemented in the Win_Strain package.62 compressibilities along the a- and c-axis of the layer plane,
Fig. 5(a) and (b) describe the pressure dependence of the tensor respectively, and suggested a compression of the layers in the
elements (numerical data are provided in Tables S1 and S2 in the direction perpendicular to the spiral chains and an expansion of
ESI†) corresponding to the compressibilities along the different the spiral chains along the helicoidal axis, similar to what occurs
axes and the direction of maximum compressibility with respect to in trigonal Se and Te.63,64
the c-axis (c) or to the a-axis (y), respectively. The reliability of our theoretical calculations allowed us
According to these figures, the a-axis (the spiral axis) is more to obtain the theoretical compressibility tensor up to 32 GPa.
compressible than the b-axis (the axis perpendicular to the layers) A sudden regularization of the three axial compressibilities to
up to 23 GPa. This is a surprising result for layered materials, roughly the same value is attained around 23 GPa, with a quick
where the axis perpendicular to the layers is usually the most change of the direction of maximum compressibility around
compressible one; however, it is coherent with the spiral chain-like this pressure. At 24 GPa, the direction of maximum compressibility
nature of the layers in orpiment and the small connectivity of the is found to be along the b-axis ([010] direction); this is the reason
why we do not display any value in Fig. 5. However, above 27 GPa,
the direction of maximum compressibility is again found to be
within the ac-plane, but now it is close to the c-axis. In
particular, C = 15(4)1 and y = 92(4)1 at 32 GPa. The drastic
change of the direction of the maximum compressibility
observed above 23 GPa can be considered as a more significant
feature of the variation of properties associated with the low-
pressure structure.
For completeness, the experimental and theoretical pressure
dependence of the axial ratios in a-As2S3 are shown in Fig. S16
in the ESI.† The monotonous trend of all the axial ratios is well
reproduced by our theoretical calculations including vdW
interactions. A closer look into the slopes reveals a clear change
of tendency above 20 GPa, where all three ratios seem to
become insensitive to pressure up to 50 GPa. A similar behavior
is observed in the pressure dependence of the b-angle (inset of
Fig. 4(b)). In some previous studies, the change in the axial
ratios of several group-15 sesquichalcogenides has been considered
as proof of the occurrence of a pressure-induced electronic
topological transition (ETT),50,65,66 since a minimum of the c/a
ratio has previously been observed to be coincident with the
occurrence of a pressure-induced ETT in a-Bi2Se3, a-Sb2Te3, and
a-Bi2Te3.67 However, in a recent work,52,68 this fact has been put
into question because the minimum of the c/a ratio can simply
originate from a change of the ratio of interlayer/intralayer forces in
Fig. 5 (a) bxx coefficients of the compressibility tensor that indicates the
layered materials. The change of the minimum of the c/a ratio does
compressibility along the different crystallographic axes. (b) Angle of
maximum compressibility c relative to the c-axis (from c to a) or equivalently
not necessarily warrant a change in the electronic density of states
y relative to the a-axis (from a to c). Solid lines represent data from calculations near the Fermi level leading to an ETT; however, it can be indicative
and symbols data from our experiments. of an IPT, as recently suggested for orpiment.33
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To prove that the change of the axial ratios is indicative of a towards sevenfold (fivefold) coordination without changing the
pressure-induced IPT, we have analyzed the pressure dependence of space group.
the internal atomic parameters of the five inequivalent atomic sites A more detailed analysis of the As polyhedral units (see
in a-As2S3 (see Fig. S17 in the ESI†). The most noticeable results are Fig. S18–S20 in the ESI†) shows how both As1 and As2 polyhedral
those observed for the three coordinates of the two inequivalent As units remain in threefold effective coordination below 10 GPa.
atoms, which show a clear trend towards certain fixed coordinates However, above this critical pressure, there is a progressive
above 18(25) GPa, as obtained for calculations without (with) vdW increase of the effective coordination up to 22 GPa, where the
interactions. This result occurs at similar pressures at which the As2 polyhedron remains in fivefold effective coordination,
change of the direction of the maximum compressibility was whereas the As1 polyhedral unit increases up to sixfold effective
observed. This result clearly indicates a modification of the HP coordination (Fig. S20 in the ESI†). We must note that in
behavior of the low-pressure phase. distorted polyhedral units (values very different from 0 in Fig. S19
A remarkable result, derived from the pressure dependence in the ESI†), the effective coordination number does not describe
of the atomic coordinates, is the grouping and regularization of properly the coordination of the polyhedral unit because some of
many theoretical As–S interatomic distances around 18 (25) GPa, the interatomic distances are longer than others, thus leading to
without (with) vdW interactions (see Fig. 6). As a consequence, effective coordination dominated by the next neighbors (Fig. S20 in
there is an increase of As1 coordination from threefold at 0 GPa the ESI†) but with large polyhedral volumes (Fig. S18 in the ESI†).
to more than fivefold (5 + 2) above 20 GPa (see Fig. 1e) because, Above 20 GPa, the effective coordination of As1 is slightly larger than
on one hand, all As1–S1 and As1–S3 intralayer distances become five despite the real coordination is higher (5 + 2). The reason for the
similar, thus giving fivefold coordination and, on the other hand, discrepancy is the strong distortion of the polyhedral unit around
two additional As1–S2 interlayer distances become smaller than As1, whereas for As2 the effective coordination (five) coincides
3 Å. Similarly, there is an increase of As2 coordination from with the real coordination due to the proximity of the interatomic
threefold at 0 GPa to fivefold above 20 GPa that stems from the distances.
equalization of the As2–S2 and As2–S3 intralayer distances. In The above results between 0 and 20 GPa are consistent with:
summary, we can conclude that above 20 GPa the As1 (As2) (i) the regularization of the axial compressibilities, (ii) the trend
polyhedral units of orpiment pass from threefold coordination towards fixed As coordinates found, and (iii) the similar x and z
Fig. 6 Evolution under pressure of the theoretical As–S interatomic distances of a-As2S3. (a) As1 and its next-neighbor S atoms. (b) As2 and its next-
neighbor S atoms. Solid (dashed) lines represent data from theoretical calculations that include (do not include) vdW interactions.
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coordinates shown by the Wyckoff sites of As1, S2, and S3 first-order PT in orpiment up to 14.5 GPa is clearly observed, in
atoms above 18(25) GPa in our calculations without (with) vdW good agreement with our HP-XRD measurements and previously
interactions. All these results indicate the presence of an IPT published results.30,33 However, the RS spectra show a much
above 20 GPa, in agreement with a recent paper33 and also with larger number of Raman modes between 2.0 and 4.1 GPa, despite
HP-XAS results that reported a change in the As environment above the disappearance of the Raman modes in the phonon gap
10 GPa and an increase of As coordination above 30 GPa.30 between 210 and 250 cm1. As already commented on, these
In summary, HP-XRD measurements and DFT calculations modes in the phonon gap, together with a mode observed above
carried out up to 32 GPa show that the effect of pressure upon 1 GPa near 120 cm1, are assumed to be second-order modes and
the structure of a-As2S3 does not result in a first-order phase will not be further discussed. No major changes of the RS spectra
transition, but triggers a change of the trend of atomic coordinates are observed between 4.1 and 14.5 GPa. In this context, it must be
and of axial ratios, and an increase of the coordination of As atoms noted that the bandgap of orpiment (2.7 eV at room pressure)
above 20 GPa, as well as a drastic change of the direction of the decreases under pressure at a rate of 0.14 eV GPa1.26,31 This
maximum compressibility above 23 GPa. All these features are means that the bandgap equals the HeNe laser energy (1.96 eV) at
in good agreement with published data30,33 and could be 5.3 GPa, so some resonance effects could be observed above
attributed to a pressure-induced IPT in orpiment above 20 GPa. ca. 4 GPa. However, there is no damage in the sample or redshift
of frequency modes after long exposure time to the laser, which
B.3 Vibrational characterization of a-As2S3 at HP indicates the lack of radiation damage in our samples.
In order to study the effect of pressure on the vibrational As already mentioned, it is very difficult to assign the features
properties of orpiment and better understand the HP behavior that show up in the room-pressure RS spectrum of a-As2S3.
of a-As2S3, we have carried out HP-RS measurements on orpiment However, it is possible to perform a tentative peak assignment
samples up to 14.5 GPa. The experimental results are compared by studying the pressure dependence of the Raman-active
to lattice-dynamics calculations of a-As2S3. In Fig. 7 we show the modes in combination with lattice-dynamics calculations on
room-temperature RS spectra of orpiment at selected pressures the basis of the correlation of the frequencies and their pressure
under hydrostatic conditions. In this figure, the absence of any coefficients (see Table 2 and Fig. 8(a)). Our observed frequencies
and pressure coefficients are in good agreement with previous
HP-RS studies.23,26,27,33 Notably, the shear or transverse rigid
modes A1g and A2g at 26 and 37 cm1 and the first Bg mode
(B2g mode) at 69 cm1 show the largest relative increase of frequency
under compression (0.24, 0.13 and 0.15 GPa1, respectively). More-
over, the B2g mode shows the experimental and theoretical largest
pressure coefficient and mode Grüneisen parameter of all Raman-
active modes (around 10.5 cm1 GPa1 and 1.97, respectively).
While the above results regarding the shear rigid layer Ag
modes are rather common in layered materials, the result
regarding the B2g mode is quite surprising because the largest
pressure coefficient is indeed expected for the compressional or
longitudinal layer mode B1g located at 62 cm1 (see Fig. S2 in the
ESI†). It is well known that the compressional layer mode
usually shows higher frequencies and pressure coefficients
than those of the shear rigid layer modes in layered materials
with vdW interactions between the layers. This common trend
is due to the extraordinary increase of the stretching force
constant between neighboring layers caused by the strong
decrease of the interlayer distance, as discussed in a recent
paper.69 However, we have found that the B1g mode in orpiment
(not observed experimentally) shows a rather small theoretical
pressure coefficient (see Table 2). This anomalous pressure
dependence of the compressional mode of orpiment can be
understood by considering a frequency anticrossing (occurring
already at room pressure) between the B1g and B2g modes. In fact,
the large pressure coefficient of the ‘‘bare’’ B1g mode (see the
dashed line in Fig. 8(b)) is so large when compared to the other
Raman modes that this mode undergoes anticrossings with
up to four Bg modes (up to B5g) in the pressure range between
Fig. 7 Room-temperature RS spectra of orpiment at selected pressures 0 and 15 GPa. This anticrossing allows us to explain the small
up to 15 GPa. pressure coefficient of the B1g mode and the large pressure
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Fig. 8 (a) Experimental (symbols) and theoretical (lines) pressure dependence of the Raman-active mode frequencies of As2S3 up to 16 GPa. The black
(red) color represents Ag (Bg) Raman-active modes. Theoretical curves correspond to calculations with vdW interactions. (b) Pressure dependence of the
theoretical Raman-active mode frequencies of As2S3 up to 36 GPa. The red dotted line represents the tentative pressure dependence of the ‘‘bare’’
B1g mode (the compressional rigid layer mode) if no anticrossing would occur with other modes of the same symmetry. Note that a change in the pressure
coefficient of the ‘‘bare’’ B1g mode is observed near 4 GPa and that a considerable softening of some vibrational modes is observed between 18 and 26 GPa.
coefficient of the B2g mode of orpiment. Moreover, this puzzling A striking feature of orpiment is the large number of Raman
behavior may explain why the compressional mode was not modes with negative pressure coefficients at room pressure.
previously assigned, despite the frequency of the compressional This is confirmed by both experimental and theoretical data. In
mode was well identified in a previous work22 as well as the particular, the modes located at 155, 291, 325, 356 and
pressure coefficient of the B2g mode.23 400 cm1 show softening under pressure in rather good agree-
As observed in Fig. 8(a), the experimental and theoretical ment with previous measurements.23,33 As noted by Besson
frequencies of the Raman-active modes do not show a simple et al.,26 negative pressure coefficients of internal modes have
monotonic behavior with increasing pressure. In fact, many been observed in Raman measurements of other chain-like
Raman modes exhibit a complex behavior under pressure with structures, such as trigonal S, Se and Te,70–72 but never for ring
crossings and anticrossings of modes with different and equal molecules, like those found in orthorhombic S.23 In trigonal S,
symmetries, respectively. This complex behavior stems from Se and Te, the soft Raman phonon is the A1 mode (the breathing
the presence of 30 Raman-active modes in a small frequency mode of the chains in the ab-plane73) and it can be related to the
region between 30 and 400 cm1, similarly to what has been expansion of the c-axis, caused by the increase of the Se–Se
found in monoclinic a-As2Te3.53 Despite the complex behavior intra-chain distance, at the expense of the contraction of the
observed in our theoretical Raman-active modes, several experi- a-axis, caused by the decrease of the Se–Se inter-chain distance.
mental modes have shown a behavior consistent with the In orpiment, the situation is quite different because all three a-,
theoretical modes. In particular, we have found an experimental b-, and c-axes suffer a contraction under compression so the
reduction of the phonon gap with pressure, an anticrossing of explanation for the negative pressure coefficients is not related
Raman modes close to 150 cm1 around 2 GPa, and the splitting to the elongation of any axis.
of several Raman modes located near 350 cm1, which are in Fig. 6 shows that the As1–S3, As2–S2, and As2–S3 (As1–S1)
good agreement with previous results.26,27,33 Such behaviors are intralayer distances increase above 0(10) GPa, thus providing
supported by our lattice-dynamics calculations for the pressure an explanation for the softening of several phonons in different
dependence of the A9g and A10 5 6
g modes, the Ag and Ag modes and pressure ranges. Notably, changes of the pressure coefficient of
12 13 14
the Ag , Ag and Ag modes, respectively (see Fig. 8(a)). some experimental and theoretical Raman-active modes have
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been observed around 4 GPa in a-As2S3, which could be

attributed to the strong changes of the interatomic distances
around these pressures. The changes can be clearly observed in
the experimental B1g and A10 g modes and in the theoretical Ag,
2
1 8 9 10 15
Bg, Ag, Ag, Ag and Ag modes (see Fig. 8(a)). They can also be
observed in the theoretical B1u, A2u, A3u, A8u, B7u, B8u and A9u modes
(see Fig. S21 in the ESI†), which do not evidence anticrossings
between 0 and 6 GPa.
Fig. 8(b) and Fig. S21 (ESI†) show a notable softening of the
theoretical vibrational modes of orpiment in the region
between 18 and 26 GPa, where the pressure-induced IPT occurs

according to our calculations. In order to probe the possibility
of a second-order IPT occurring in a-As2S3, we have studied the
phonon dispersion curves calculated at different pressure
values, ranging up to 30 GPa (see Fig. S22 and S23 in the ESI†),
because a second-order IPT is related to the presence of a soft
phonon mode according to Landau theory. Since we do not
observe any soft mode up to 30 GPa, we can conclude that the
pressure-induced IPT occurring in a-As2S3 above 20 GPa must
be of order higher than 2, i.e. an IPT of electronic origin, such
as the pressure-induced ETTs observed in other group-15
sesquichalcogenides.67
Fig. 9 Calculated band structure of As2S3 at different pressures: (a) 0 GPa,
In summary, HP-RS measurements and lattice-dynamics (b) 5 GPa, (c) 10 GPa, (d) 15 GPa, (e) 20 GPa, and (f) 30 GPa.
calculations on orpiment carried out up to 37 GPa show that
the lattice-dynamics of orpiment at HP is quite complex and
has a large number of optical modes with negative pressure recent ab initio calculations, however differing in the precise
coefficients, related to the increase of some As–S bond dis- locations of the VBM and CBM.33,55
tances, which cause a decrease of the phonon gap in orpiment There are considerable changes in the VBM and CBM of
under compression up to 20 GPa. Above this pressure, most a-As2S3 at HP. Both the valence and conduction bands show low
phonons show a positive pressure coefficient, thus showing a dispersion across the BZ at 0 GPa, but high dispersion above
complete change in the behavior of the phonons of orpiment 20 GPa. The flat bands at 0 GPa reflect the 2D character of
below and above 20 GPa; however, no soft modes going to zero orpiment, while the highly-dispersed bands above 20 GPa reflect
frequency have been observed according to Landau theory so the 3D character of orpiment above this pressure. It can be
we can conclude that the IPT near 20 GPa is not of second-order observed that above 20 GPa, the VBM shifts to the G-point and
but of higher order, i.e. of electronic origin. Moreover, we have along the G–B direction, whereas the CBM moves to the B-point.
provided a tentative assignment of the Raman- and IR-active Additionally, a variation of the VBM occurs between 20 and
modes that can help in studying orpiment in ancient artworks using 30 GPa, with the VBM at 30 GPa shifted along the high-symmetry
non-destructive techniques such as Raman and IR spectroscopy.39 G–Y direction. Since we observe the crossing of an extremum
through the Fermi level above 20 GPa, thus modifying the topology
B.4 Electronic band structure calculations of a-As2S3 at HP of the Fermi-surface, we thus suggest a possible pressure-induced
To complete the picture of the behavior of orpiment at HP and ETT above this pressure in a-As2S3.
in order to assess whether a pressure-induced ETT could be The calculated indirect bandgap exhibits a strong decrease
observed in orpiment, we have performed ab initio electronic at HP from 1.7 eV at 0 GPa to 0 eV at 26 GPa (see the solid line in
band-structure calculations of a-As2S3 at different pressures to Fig. 10). Therefore, our calculations provide evidence for a
identify possible changes of the band extrema that could be semiconducting–metallic transition in orpiment above 26 GPa.
related to a pressure-induced ETT (see Fig. 9). Our calculations A recent experiment suggests that metallization in orpiment
show that orpiment is an indirect bandgap (1.7 eV) semi- should occur above 42 GPa.33 If we assume that metallization
conductor at 0 GPa, with the valence band maximum (VBM) occurs in the monoclinic P21/n phase around 42 GPa, the under-
and conduction band minimum (CBM) being located along the estimation of the bandgap by our DFT calculations would be only
high-symmetry segment of the Y–G and G–Z directions, respec- 0.3 eV (see the long dashed line in Fig. 10); however, if we take
tively. The value of the bandgap is clearly underestimated by into account the value of the experimental bandgap at room
our DFT calculations, since orpiment is known to have a pressure (2.7 eV), i.e. assuming an underestimation of the
bandgap around 2.7 eV at room pressure,26,31 but the structure bandgap of 1.0 eV, and shift the calculated bandgap to match
of the electronic bands and the bandgap evolution with pressure the latter, the evolution of the bandgap (see the short dashed line
are correctly described by this method. The bandgap energy in Fig. 10) agrees remarkably well with the behavior of the optical
value in our calculations is similar to the values reported by bandgap (symbols in Fig. 10).26,27 In fact, the decrease of the
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order to distinguish it from the resonant bonding occurring in

benzene and graphite.44 In particular, we will show that the HP
behavior of orpiment between 0 and 20 GPa can be considered
as the process of change from p-type covalent bonding towards
metavalent bonding at HP. Moreover, we will show that the concept
of metavalent bonding could be extended to understand the
pressure behavior of other group-15 sesquichalcogenides and of
trigonal Se and Te.
Metavalent bonding is a recently proposed new class of
bonding formalism, mainly located between p-type covalent
bonding and metallic bonding, which is characteristic of a new

type of materials termed ‘‘incipient metals’’.44 This kind of
bonding occurs in materials where there is a deficiency of valence
electrons in the unit cell, forming a large number of bonds, such
Fig. 10 Pressure dependence of the energy bandgap of orpiment. Solid, as in octahedrally-coordinated rocksalt-related structures like
long dashed and short dashed lines correspond to results of theoretical those found in GeTe, SnTe, PbSe, PbTe, Sb, Bi, Sb2Te3, Bi2Se3,
calculations including vdW interactions, theoretical calculations shifted by Bi2Te3, AgSbTe2, AgBiSe2, AgBiTe2, and GeSb2Te4.41,44,45 Under
0.3 eV (to match the metallization observed above 42 GPa in ref. 33) and these circumstances, the few valence electrons available in the
theoretical calculations shifted by 1.0 eV (to match the optical bandgap at
formula unit must be shared (resonate) between several bonds in
0 GPa as in ref. 26 and 27), respectively. Symbols correspond to experi-
mental data from ref. 26 and 27. order to provide the most symmetrical structure, i.e. with the
largest number of similar bonds and with the largest possible
cation coordination (highest packing), compatible with the valence
electronic bandgap shows a theoretical pressure coefficient of electrons available and strain limitations, e.g. those imposed by
0.16 eV GPa1, which is in very good agreement with a previous stereoactive LEPs.75–77
experimental estimation of the optical bandgap pressure coeffi- The main characteristics of metavalent bonding are: (i) cation
cient (0.14 eV GPa1).26,27,31 Assuming the 1.0 eV bandgap coordination much higher than that assumed with the 8-N rule;
underestimation of our calculations, the extrapolation of the (ii) high Born effective charges that are much larger than the
shifted calculated bandgap to 0 eV yields a closure of the bandgap valence of the atoms; (iii) higher optical dielectric constants than
of the monoclinic P21/n phase at pressures that go beyond typical covalent materials; (iv) high mode Grüneisen parameters
the studied range (above 50 GPa). This result suggests that the of phonons and lower wavenumbers of optical phonons than
observed metallization at 42 GPa33 could be explained by the non- typical covalent materials, thus revealing a high lattice anharmoni-
hydrostatic conditions in the sample during electric measurements city causing a very small thermal conductivity; and (v) a moderately
or by a phase transition towards another phase. In this context, we high electrical conductivity caused by a very small bandgap. All
have found a triclinic P1% phase that is energetically more favorable these features stem from the partial delocalization of electrons that
than the P21/n phase above 40 GPa (see the enthalpy vs. pressure plot are shared between several bonds. Due to these characteristics,
in Fig. S24, ESI†). This result suggests that the existence of a phase materials featuring metavalent bonding have been named
transition towards a metallic phase of As2S3 above 40 GPa is possible ‘‘incipient metals’’ because they show characteristics close to
in good agreement with ref. 33. those of metals. In fact, they exhibit extraordinary properties
In summary, our calculations show that a-As2S3 is a semi- that make them ideal candidates for phase-change materials,
conductor with an indirect bandgap (B2.7 eV at room pressure) thermoelectric materials, and topological insulators.
that decreases at HP at an initial rate of B0.16 eV GPa1 and Regarding orpiment, the equalization of the As–S intralayer
becomes a metal well above 50 GPa. These features are in distances above 18(25) GPa according to our calculations with-
perfect agreement with already reported optical absorption out (with) considering vdW interactions is in agreement with
measurements. Besides, we observe a clear change in the the bonding variation nature of As–S bonds from covalent to
VBM above 20 GPa that could lead to a pressure-induced ETT, i.e. metavalent.43–45 To prove such a fact, we have probed the
an IPT of order 21/2 according to Ehrenfest notation.74 Furthermore, bonding character of orpiment at different pressures, e.g. the
we propose that there could be a possible first-order phase electron localization function (ELF) along the seven next-neighbor
transition in orpiment above 40 GPa to a metallic phase that As–S distances, the dielectric tensor, and the Born effective charges,
would explain the recent results on HP electrical measurements.33 as suggested in ref. 44.
The increase of the metavalent bonding in orpiment under
B.5 Metavalent bonding in a-As2S3 compression can be traced by the increase of the theoretical
In this section, we will show that the results obtained so far for dielectric constants and the Born effective charges (see Fig. 11),
the pressure dependence of the structural, vibrational, optical as commented on in ref. 40 and 44. A strong increase in the
and electric properties of a-As2S3 can be understood in the light absolute value of most of these magnitudes is observed between
of a special case of resonant bonding formalism.40–45 This 0 and 20 GPa.78 The only Born effective charge component that
bonding has recently been termed as metavalent bonding in does not show similar behavior within the range of 0 and 20 GPa
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the three bonds of each As atom (As1–S1, As1–S2, As1–S3,

As2–S1, As2–S2, and As2–S3), thus evidencing the threefold
coordination of As1 and As2 atoms and the covalent bonding
in orpiment at room pressure. However, at 25 GPa there are five
intralayer As2–S bonds with high ELF values (an As2–S1 bond
above 0.8 and two As2–S2 and two As2–S3 bonds above 0.6)
showing fivefold coordination for As2 in orpiment. A similar
situation occurs for the As1 atoms at 25 GPa, with five intralayer
As1–S bonds with a relatively high ELF (an As1–S2 bond near
0.8, two As1–S1 above 0.7 and two As1–S3 above 0.5), but also
with two interlayer As1–S2 bonds with an intermediate value of

the ELF (slightly above 0.2), which can be considered to support
5 + 2 coordination. Note that the typical metavalent bonding in
the layer plane (ac-plane) of orpiment is clear for the As2 atoms,
where all four intralayer bonds (As2–S2, As2–S3, As2–S4, and
As2–S5) have the same ELF value because they have the same
Fig. 11 Pressure dependence of the static dielectric function along the
main crystallographic axes (a) and Born effective charges of the different
As2–S length. On the other hand, the character of the As1–S
As1, As2, S1, S2 and S3 atoms along the main crystallographic axes (b–d). bonds is more complex because the ELF values and lengths of
all the intralayer bonds are not equal. Such behavior suggests
that the intralayer metavalent bonding of As1 atoms is sacrificed
is the Zzz component, which is related to the c-axis, the direction by a larger coordination number taking into account the S atoms
of the smallest change in bonding character because it is the of adjacent layers. Note that these S atoms are not linked to the
direction of smaller compressibility (see Fig. 5). These changes As2 atoms of the monoclinic structure even up to 50 GPa, what
are a clear indication of the decrease (increase) of the covalent evidences the different behavior of As1 and As2 atoms on
(metavalent) bonding of the layers of orpiment. Besides, the increasing pressure. The larger coordination of As1 atoms at
strong decrease of the optical bandgap with pressure and the HP is indicative of a tendency of As1 atoms towards metallic
metallization of orpiment well above 50 GPa are consistent bonding, which is usually characterized by a much larger effective
with the metavalent bonding observed for chalcogenides.44,45 coordination number than covalent and metavalent bonding.44,45
The rapid delocalization of the electron charge density over the The decrease of the bond force (ELF value) of some As–S
plane of the layers caused by the steep increase of coordination bonds in orpiment is likely related to the length increase of
of As atoms due to the strong compression of the chains mainly those bonds (see Fig. 6), because the charge of valence electrons
along the a-axis is the origin of the pronounced negative slope of in As atoms must progressively be redistributed among several
the bandgap with increasing pressure. equidistant As–S bonds within the context of metavalent
Similarly to what was done with GeSe to study the pressure bonding.44,45 Therefore, the charge at each of the short bonds
dependence of the Ge–Se bonds,43 we plot in Fig. 12 the ELF at low pressure is redistributed between two equal bonds at HP
values along the seven next-neighbor As1–S and As2–S dis- leading to a smaller ELF for the initial short bonds at HP than
tances obtained from our theoretical results at 0 and 25 GPa. room pressure. Such a feature is confirmed by the equal values of
At 0 GPa, both the As1 and As2 atoms have high ELF values the ELF in As–S bonds of equal length at HP already commented
(around 0.8) close to the center of the As–S bonds for each of on. Therefore, the decrease of the ELF of the original covalent
bonds at HP clearly shows the delocalization of electronic charge
in these bonds to form metavalent bonds at HP.
This bond enlargement and charge redistribution typical of
the formation of metavalent bonds are expected to cause a
decrease of some of the optical phonon frequencies. In particular,
a softening of the transverse optical (TO) and longitudinal optical
(LO) modes has been predicted in rocksalt compounds with
metavalent bonding as compared to the same compound in the
absence of metavalent bonding.41,42 For a monoclinic compound,
such as orpiment, the situation is more complex, because the TO
and LO modes of the rocksalt structure are split into many
components due to the decrease in symmetry. Therefore, we expect
that many optical modes of orpiment will soften with increasing
pressure due to the establishment of long-range interactions
between neighboring atoms upon increasing the metavalent
Fig. 12 Pressure dependence of the ELF along the As1–S (top) and As2–S bonding at increasing pressure. In fact, Table 2 and Fig. 8 show
(bottom) bonds at 0 GPa (a) and 25 GPa (b). that one of the most characteristic modes that exhibit a negative
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pressure coefficient is the A10 g mode (see atomic vibrations in An intermediate case between covalent and metavalent
Fig. S11 in the ESI†), which is experimentally observed at bonding is also that of a-As2Te3, which shows an average cation
291 cm1 at room pressure. Other soft Raman- and IR-active coordination of 5.5, because one cation has 3 + 2 coordination
modes can be observed in Fig. 8(b) and Fig. S21 in the ESI,† and the other has 3 + 3 coordination. Therefore, it shows inter-
respectively. Moreover, these last figures show a clear decrease mediate coordination between the fivefold coordination of
of the phonon bandgap (between A9g and A10 g and between Bu
7
a-Sb2Se3 and the sixfold coordination of a-Sb2Te3. Consequently,
8
and Bu) from 0 to 20 GPa. This decrease of the phonon bandgap a-As2Te3 shows almost no soft phonons. Only a few high-
is also expected in the context of metavalent bonding.41,42,44 frequency phonons show soft behavior with an almost negligible
Finally, we observed a considerable softening of several modes pressure coefficient between 0 and 4 GPa and a notable hard-
taking place between 18 and 26 GPa and clear positive slopes of ening above this pressure.53 An inspection of the evolution of the
most vibrational modes above 26 GPa, i.e. once the bonding As–Te distances in this pressure range shows that the As1 (As2)
transition to metavalent bonding takes over. These features are coordination changes from almost five (six) at room pressure to
in agreement with the development of metavalent bonding real six (six) above 4 GPa. Therefore, the changes observed in
since low-frequency values of optical vibrational modes and the pressure coefficients of the zone-center vibrational modes
positive slopes of all Raman-active and IR-active modes have in a-As2Te3 are indicative of a change of bonding type from
been observed in Bi2Se3, Sb2Te3 and Bi2Te3, which are metavalent almost metavalent bonding inside the layers to full metavalent
compounds at room pressure.67 bonding that takes into account also interactions between
A closer look into the HP behavior of other chalcogenides the layers. Finally, b-As2Te3 with R3% m symmetry and sixfold
evidences that the softening of optical modes at HP has been coordination has been confirmed to show metavalent bonding81
observed in a number of chalcogenides, thus suggesting that and is expected to show no soft modes like a-Bi2Se3, a-Bi2Te3
metavalent bonding is more common than expected at HP in and a-Sb2Te3.67
these compounds. Several modes of the low-pressure trigonal It must be noted that a notable decrease of the bandgap
phase of Se and Te exhibit a pronounced softening at HP. with pressure has also been obtained in DFT calculations for
However, no softening has been found in the HP phases of these a-Sb2S3, a-Sb2Se3 and a-Bi2S3,52 and at a smaller rate also for
two elements,79,80 as happens in Bi2Se3, Bi2Te3 and Sb2Te3.67 a-As2Te367 and Bi2Te3.82 In fact, we have observed metallization
This result is consistent with the recent confirmation of the around 26 GPa in our DFT calculations for a-As2S3, similar to
metavalent bonding in Bi2Se3, Bi2Te3 and Sb2Te3 and b-As2Te3 at the metallization found around 4 GPa for a-As2Te3 and above
room conditions81 and with the formation of metavalent bonding 12 GPa for a-Sb2S3. Therefore, it is expected that a similar
in Se and Te at HP.44 Therefore, we expect a similar increase of increase of the dielectric tensors and the Born effective charges at
dielectric constants and Born effective charges at HP in the low- HP occurs in these group-15 sesquichalcogenides, thus supporting
pressure trigonal phase of Se and Te, as has been shown in the occurrence of metavalent bonding in these compounds at HP.
orpiment and other compounds.40,44,45
Finally, we want to emphasize that the analysis of the different
group-15 sesquichalcogenides (Table S3 in the ESI†) reveals that C Experimental and theoretical
their behavior at HP can also be understood in the framework of description
metavalent bonding. In particular, some of these materials possess
metavalent bonding at room pressure81 and our work shows that C.1 Experimental details
some others tend to metavalent bonding at HP. For instance, Almost pure mineral orpiment from Hunan province (China)
a similar situation to that of a-As2S3 is expected to occur was used in the present study. Angle-dispersive powder HP-XRD
for isostructural a-As2Se3 and for b-As2Se3 at HP since both experiments at room temperature up to 25 GPa were conducted
compounds feature threefold coordination at room pressure. in a membrane-type diamond anvil cell (DAC) at the BL04-MSPD
Unfortunately, there are almost no HP studies of these compounds. beamline of the ALBA synchrotron. The incident monochromatic
On the other hand, a-Sb2S3, a-Sb2Se3 and a-Bi2S3, which crystallize beam with a wavelength of 0.4246 Å was focused to 20 20 mm2
in the orthorhombic Pnma phase, feature average fourfold cation using a pinhole of 50 mm to cut the X-ray beam tail.83 Images
coordination, because one cation has threefold coordination covering a 2y range up to 181 were collected using a SX165 CCD
and the other has fivefold coordination. Therefore, they located at 240 mm from the sample. One-dimensional diffraction
show intermediate cation coordination between the threefold profiles of intensity as a function of 2y were obtained by integration
coordination of a-As2S3 and the sixfold coordination of a-Sb2Te3. of the observed intensities with the Fit2D software.84 Le Bail
They exhibit softening of some high-frequency modes.50–52 In refinements were carried out with the GSAS software package
particular, softening of two high-frequency modes has been for synchrotron measurements.85,86 Interatomic distances were
observed in a-Sb2S3 up to 12 GPa, a pressure at which Sb1 and obtained with the Visualization for Electronic and Structural
Sb2 can be considered to have almost sevenfold coordination due Analysis (VESTA) software.87 The EoS of copper,88 which was mixed
to pressure-induced metavalent bonding of both Sb atoms.52 with the sample powder, was used for pressure calibration.
These compounds have been recently shown not to be metavalent Room-temperature unpolarized HP-RS measurements up to
at room pressure,81 becoming metavalent at HP according to 14.5 GPa were carried out with a Horiba Jobin Yvon LabRAM
our work. HR spectrometer equipped with a thermoelectrically cooled
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multichannel CCD detector. RS measurements with a spectral temperature and HP and have found that orpiment undergoes
resolution better than 2 cm1 were performed using the 632.8 nm strong compression up to 20 GPa, followed by an IPT of
line of a He:Ne laser with a power below 1 mW in order to avoid electronic origin, which leads to a coordination of As which is
laser heating of the sample. The use of an edge filter limited the higher than five above that pressure. The most striking feature
observation of Raman-active modes below 40 cm1. The pressure of the pressure-induced IPT is that several As–S bond distances
was determined with the ruby fluorescence method.89 In both become equal above 20 GPa.
HP-XRD and HP-RS measurements, a methanol–ethanol (4 : 1 ratio) The lattice dynamics of orpiment has been studied and all
mixture was used as a pressure-transmitting medium with the rigid layer modes and the main inter-chain and intra-chain
quasi-hydrostatic conditions up to 10 GPa and the deviatoric modes have been fully described. Our measurements and
stresses are within the experimental uncertainty of this soft calculations evidence the softening of many vibrational modes
material up to 25 GPa.90,91 and the decrease of the phonon gap (it closes above 20 GPa) at
HP. Moreover, our calculations confirm the metallization of
C.2 Theoretical details orpiment above 26 GPa due to the strong decrease of the optical
Ab initio calculations within DFT92 were performed to compute bandgap, thus supporting metallization in the laboratory under
the electronic and structural properties of a-As2S3 by using the hydrostatic conditions well above 50 GPa when taking into
plane-wave Vienna Ab initio Simulation Package (VASP).93,94 consideration the underestimation of the energy bandgap in
The projector-augmented wave scheme (PAW)95 was considered DFT calculations. All these changes are related to the formation
to treat the valence and the semi-core states more explicitly by of metavalent bonding occurring in orpiment above 20 GPa due
including the 4s and 4p outermost electrons of As and the 3s to the delocalization of electronic clouds, mainly in the
and 3p electrons of S as valence electrons, with the remaining ac-plane of the layers, leading to an increase of cation coordination
electrons being considered frozen at the core. In this work, the (more than fivefold) without the need for a first-order structural
generalized gradient approximation with the Perdew–Burke– phase transition as in Se and Te, and similar to GeSe upon the
Ernzerhof (PBE)96 parametrization was used for the exchange Pnma to Cmcm phase transition.43
and correlation energy, after evaluating calculations performed On top of that, we have suggested that metavalent bonding
also with the PBEsol modified version97 in ref. 35. The plane- already occurs in other group-15 sesquichalcogenides at room
wave kinetic-energy cutoff was defined as 360 eV, which pressure or at HP. Full metavalent bonding occurs in topological
together with the use of a dense Monkhorst–Pack grid98 with insulators and good thermoelectric materials such as a-Bi2Se3,
a 6 4 2 k-point reciprocal space sampling mesh ensured a a-Bi2Te3 and a-Sb2Te3 with tetradymite layered structure that
convergence of the total energy of around 1 meV with deviations feature sixfold cation coordination. In these compounds, trans-
of the stress tensor from a diagonal hydrostatic form of less formation from metavalent to metallic bonding occurs at HP
than 1 kbar (0.1 GPa). The vdW corrections to the total energy (still not proved for b-As2Te3) after a first-order phase transition
were taken into account within DFT by using the D2 method.99 to a structure with cation coordination larger than the original
Electronic band-structure calculations were carried out at sixfold-coordinated one. On the other hand, partial metavalent
different pressures along selected high-symmetry k-points on bonding occurs in a-Bi2S3, a-Sb2S3 and a-Sb2Se3, with an orthor-
the first BZ. Additionally, analysis of the electron density hombic Pnma structure, and in a-As2Te3. These compounds
topology and of the ELF was accomplished with the VESTA show intermediate coordination between three and six. In all
program employing data from the VASP code.100,101 these compounds, pressure increases the cation coordination,
Lattice-dynamics calculations were performed at the zone leading to a considerable bandgap reduction and partial phonon
center (G-point) and along high-symmetry segments of the BZ softening consistent with metavalent bonding at HP. Finally, we
as a function of pressure, by using the direct-force constant predict that a similar situation to that for As2S3 is expected for
approach.102,103 The separate calculations of the forces which As2Se3 polymorphs and also in the low-pressure trigonal Se and
result from a fixed displacement away from equilibrium of the Te at HP. These compounds featuring threefold coordination
atoms in the primitive cell necessary for the construction of the at room pressure are expected to exhibit metavalent bonding
dynamical matrix at the G-point of the BZ were achieved with at HP.
VASP. The diagonalization of the dynamical matrix provides the In summary, our present results on a-As2S3 confirm that
normal-mode frequencies and allows identifying the irreducible pressure is able to tune the metavalent bonding in group-15
representations and the character of the vibrational phonon sesquichalcogenides, such as occurs for orpiment, thus turning
modes at the G-point. common semiconductors into ‘‘incipient metals’’ with pro-
mising phase-change, thermoelectric and topological insulating
properties at extreme conditions. Since Sb2Te3 and Bi2Te3 are
D Conclusions topological insulators and two of the best known thermoelectric
materials at room conditions due to metavalent bonding,81 this
The monoclinic structure of orpiment (a-As2S3) at room conditions work paves the way to design new group-15 sesquichalcogenides
is composed of layers formed by AsS spiral chains, where the As and related compounds with thermoelectric or topological
atoms have threefold coordination. We have studied the structural, insulating properties both at room pressure and at extreme
vibrational, and electronic properties of orpiment at room conditions.
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Paper PCCP
Conflicts of interest 14 H. F. Cheng, Y. Zhou and R. L. Frost, Spectrosc. Lett., 2017,

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Paper: Orpiment Under Compression: Metavalent Bonding at High Pressure

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Orpiment under compression: metavalent

Cite this: Phys. Chem. Chem. Phys.,

Rosario Vilaplanab and Francisco Javier Manjón *a

The theoretical atomic parameters of the five inequivalent

where g (gerade) modes are Raman-active (R) and u (ungerade)

Lattice Experimental Theoretical Experimental Experimental Theoretical Theoretical

B3g 94 (2) 3.1 (1) 103 (2) 2.9 (1)

Fig. 4 (a) Experimental (symbols) and theoretical (solid lines) pressure

and the order of the BM-EoS was determined by the monoto-

been observed around 4 GPa in a-As2S3, which could be

between 18 and 26 GPa, where the pressure-induced IPT occurs

order to distinguish it from the resonant bonding occurring in

bonding and metallic bonding, which is characteristic of a new

the three bonds of each As atom (As1–S1, As1–S2, As1–S3,

with two interlayer As1–S2 bonds with an intermediate value of

Conflicts of interest 14 H. F. Cheng, Y. Zhou and R. L. Frost, Spectrosc. Lett., 2017,

173, 185–191. 2007, 126, 084503.

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