ACTA PHYSICA POLONICA A No. 2 Vol.

140 (2021)

Calculation of Vibrational
Frequencies of Sulfur Dioxide
by Lie Algebraic Framework

M.R. Ballaa , S. Venigallab and V. Jaliparthic,∗

a
Department of Physics, School of Science, GITAM Deemed-to-be-University,
Rudraram, 502329, Hyderabad, India
b
Department of Chemistry, A.G.& S.G. Siddhartha Degree College of Arts & Science,
Vuyyuru, 521165, Vijayawada, India
c
Department of Mathematics, School of Science, GITAM Deemed-to-be-University,
Rudraram, 502329, Hyderabad, India

Received: 05.05.2021 & Accepted: 20.07.2021

∗
Doi: 10.12693/APhysPolA.140.138 e-mail: vijayjaliparthi@gmail.com

In this paper, we have demonstrated the application of the U(2) Lie algebraic method to predict the
vibrational frequencies of sulfur dioxide (SO2 ). A Hamiltonian that preserves the C2ν point group sym-
metry of the molecule is devised using three interacting Morse oscillators. Root mean square deviation
of the calculated vibrational frequencies is found to be 1.054 cm−1 with reference to their experimental
values. This asserts that the U(2) Lie algebraic method is successful in calculating the fundamental
vibrational frequencies, and their higher overtones near to the spectroscopic level of accuracy.
topics: vibrational frequencies, sulfur dioxide, U(2) Lie algebraic method

1. Introduction approaches. The lesser computational cost of the

Lie algebraic framework is evident from the lesser
Theoretical calculations of vibrational frequen- demand of computational time for performing al-
cies of polyatomic molecules have been one of the gebraic manipulations, rather than integration and
interesting research areas for scientists on account differentiation of the potential function as in other
of the development of innovative spectroscopic tech- approaches [1, 2].
niques. The investigation of vibrational spectra of
molecules has been improved in recent years both 2. The U(2) Lie algebraic method
theoretically and experimentally. Two approaches
have been predominantly used so far in the study Sulfur dioxide (SO2 ) is a bent triatomic molecule
of experimental spectra: the well-known Dunham- with the equilibrium structure belonging to the C2ν
like expansion of energy levels in terms of rotation– point group symmetry. The molecule is non-linear
vibration quantum numbers and the solution of the with 3 vibrational degrees of freedom. Each of the
Schrödinger equation with potential functions. vibrating bonds in SO2 molecule is effectively de-
In this work, we applied the Lie algebraic method scribed by a one-dimensional Morse oscillator and
to study the vibrational frequencies of sulfur diox- is assigned with a corresponding U(2) Lie algebra,
ide. This method reformulates the Hamiltonian op- as per the schematic shown in Fig. 1.
erator in terms of elements of the Lie algebra and The two possible chains of dynamical symmetry
provides the same physical information as that of groups in SO2 molecule, corresponding to the local
the Dunham and potential approaches [1, 2]. The and normal couplings in stretching vibrations, are
advantage of the proposed method, as compared to given by
local
that of the Dunham or potential approach, is that U1 (2) ⊗ U2 (2) ⊃ O1 (2) ⊗ O2 (2) → coupling (1)
usually fewer parameters are required to get the
normal
same level of accuracy, in contrast to their com- U1 (2) ⊗ U2 (2) ⊃ U12 (2) ⊃ O12 (2) → coupling (2)
parators [3, 4]. The Lie algebraic method makes it The interaction results in three normal mode vi-
possible to predict the vibrational frequencies much brations ν1 , ν2 , and ν3 , correspond to the symme-
more accurately and possibly at a much lesser com- try species A1 (symmetric stretch), B1 (asymmetric
putational cost as compared to other theoretical stretch), and A1 (bend).

138
 Calculation of Vibrational Frequencies of Sulfur Dioxide. . .

hNi , νi ; Nj , νj |Mij | Ni , νi ; Nj , νj i =

(Ni νj + Nj νi − 2νi νj ) ,

hNi , νi + 1; Nj , νj − 1 |Mij | Ni , νi ; Nj , νj i =
q
− νj (νi + 1) (Ni − νi ) (Nj − νj + 1),

hNi , νi − 1; Nj , νj + 1 |Mij | Ni , νi ; Nj , νj i =
q
− νi (νj + 1) (Nj − νj ) (Ni − νi + 1), (6)
where νi (i = 1, 2, . . .) are the vibrational quan-
Fig. 1. Assignment of U(2) Lie algebras for bonds
tum numbers. The vibron number Ni (i = 1, 2) for
in SO2 molecule.
(S–O) stretching bonds of the molecule are calcu-
lated by the following relation [7]:
ωe
 The local vibrational basis is constructed as + Ni = − 1. (7)
 U (2) ⊗ U (2) ⊗ U (2) ⊃ O (2) ⊗ O (2) ⊗ O (2)
 1 2 3 1 2 3
ωe xe

 N1 N2 N3 ν1 ν2 ν3 Here, Ui (2) are the spectroscopic constants [8] and
1 6 i 6 3. The initial guess value for the param-
(3) eter Ai (i = 1, 2) is obtained by using the energy
keeping
P the total vibrational quantum number equation for the single-oscillator fundamental mode.
V = i=a,b,c νi always a conserved quantity. It is given as [9–11]:
The Hamiltonian operator that describes the vi- E (ν = 1) = −4Ai (Ni − 1) . (8)
brational spectra of the two interacting single bonds Initial guesses for Aij are taken as zero. The pa-
(S–O) in SO2 molecule are expressed mathemati- rameter λij is determined from the relation [1, 2]:
cally as [5, 6]: |Ei − Ej |
n n n λij ' . (9)
X X X 2N
H = E0 + Ai Ci + Aij Cij + λij Mij . To get accurate results, a numerical fitting proce-
i=1 i<j i<j dure is essential to obtain the parameters Ai , λij
(4) (when i, j = 1, 2, and i 6= j) starting from values as
Here, E0 is the electronic ground state energy of given by (8) and (9).
the bond S–O, which will be taken as the zero ref-
erence
Pn for all the vibrational excitations. The term
3. Results
i=1 Ai Ci corresponds to the independent local os-
cillators expressed using
Pn the invariant Casimir oper-
ators Ci . The term i<j Aij Cij is accounted for the Our calculations based on the constructed Lie
cross-anharmonicities between pairs of distinct local algebraic Hamiltonian, followed by the linear re-
oscillators in terms P of the coupled Casimir opera- gression analysis (fitting procedure) resulted in the
n
tors Cij . The term i<j λij Mij expresses the an- optimized algebraic parameters, which are given
harmonic, non-diagonal interactions involving the in Table I.
pairs of local oscillators in terms of the coupled The calculated vibrational frequencies in funda-
Majorana operators Mij . The eigenvalues of the mental, overtone and their combinations are pre-
Hamiltonian can be evaluated and give a descrip- sented in Table II.
tion of n coupled anharmonic vibrations. The cou-
plings in the Hamiltonian are only first order, in TABLE I
the sense that the Majorana operators Mij annihi-
late one quantum of vibration in bond j, and create Optimised fitting parameters. Note: N1 , N2 , and N3
are dimensionless numbers.
one in bond i (or vice versa).
Here, i varies from 1 to 2 for the two (S–O) U(2) Lie algebraic Vibrational
Optimised value
stretching bonds. The algebraic parameters model parameters mode
{Ai , Aij , λij } are calculated from the spectroscopic N1 , N2 178 stretching
data of S–O single bond. The invariant oper- N3 88 bending
ator Ci of the uncoupled bond with eigenvalues
−4(Ni νi − νi2 ) and the operator Cij for coupled A1 , A2 −2.2799 cm−1 stretching
bonds are diagonal with matrix elements A3 −2.2297 cm−1 bending
hNi , νi ; Nj , νj |Cij | Ni , νi ; Nj , νj i = A12 , A21 0.3262 cm−1 stretching
2
A13 , A23 0.3699 cm−1 bending
4 (νi + νj ) − (νi + νj ) (Ni + Nj ) , (5)
λ12 , λ21 0.5905 cm−1 stretching
while the Majorana operator Mij has both diagonal
λ13 , λ23 2.9425 cm−1 bending
and non-diagonal matrix elements

139
 M.R. Balla et al.

TABLE II References
Vibrational frequencies of sulfur dioxide.
[1] S. Oss, Adv. Chem. Phys. 93, 455 (1996).
Vibrational Vibrational frequencies [cm−1 ] [2] F. Iachello, R.D. Levine, Algebraic Theory
mode Experiment [12, 13] U (2) Lie method of Molecules, Oxford University Press, Ox-
(1 0 0) 1151 1150.9652 ford 1995.
(0 0 1) 1361.2 1361.1832 [3] N.K. Sarkar, Mol. Phys. 119, e1836409
(0 1 0) 517 517.8944 (2021).
(2 0 0) 2295.9 2294.9032 [4] S.R. Karumuri, K.G. Sravani, J. Vi-
(0 0 2) 2714 2715.6130 jayasekhar, L.S.S. Reddy, Acta Phys. Pol.
A 122, 1111 (2012).
(0 2 0) 1034.9 1035.7744
[5] M.R. Balla, V.S. Jaliparthi, Mol. Phys.
(3 0 0) 3435.4 3437.0171
115, e1828634 (2021).
(0 0 3) – 4056.5053
[6] F. Iachello, Chem. Phys. Lett. 78, 581
(0 3 0) – 1553.6544
(1981).
(4 0 0) – 4558.1320
[7] F. Iachello, R.D. Levine, J. Chem. Phys.
(0 0 4) – 5403.2261 77, 3046 (1982).
(0 4 0) – 2071.5344
[8] K.K. Irikura, J. Phys. Chem. Ref. Data
(5 0 0) – 5758.4300 36, 389 (2007).
(0 0 5) – 6845.2126 [9] F. Iachello, S. Oss, J. Mol. Spectrosc. 142,
(0 5 0) – 2589.4144 85 (1990).
(6 0 0) – 6815.3209 [10] F. Zhaochi, G. Xiong, Y. Qihua, Q. Xin, Li
(0 0 6) – 8287.0553 Can, Chin. Sci. Bull. 44, 1961 (1999).
(0 6 0) – 3107.2944 [11] M.R. Balla, V.S. Jaliparthi, “Vibrational
(1 0 1) 2499.1 2514.758 Hamiltonian of Naphthalene (C10 H8 )
(2 0 1) – 3658.696 Using Dynamical U(2) Lie Algebras”,
(1 0 2) 3837 3869.1878 Polycycl. Aromat. Compd., (2021).
(3 0 1) – 4800.8099 [12] W.S. Benedict, N. Gailar, E.K. Plyler,
(1 0 3) – 5210.0801 J. Chem. Phys. 21, 1301 (1953).
(4 0 1) – 5921.9248 [13] W.S. Benedict, N. Gailar, E.K. Plyler,
(1 0 4) – 6556.8009 J. Chem. Phys. 24, 1139 (1956).
(5 0 1) – 7122.2228
(1 0 5) – 7998.7874
(2 0 2) – 5013.1258
(3 0 3) – 7496.132

4. Conclusion

Vibrational frequencies of sulfur dioxide are cal-

culated using the U(2) Lie algebraic method, and
the calculated frequencies are compared with the
reported experimental data. The results obtained
are found to be consistent with the experimental
results, indicating that our approach can be ap-
plied to study the vibrational spectra of a variety
of molecules. The obtained results confirm that the
U(2) Lie algebraic framework has successfully re-
produced the vibrational frequencies at the funda-
mental excitations near to the level of spectroscopic
accuracy, as well as predicted their first five over-
tones.

140