Article

pubs.acs.org/JPCA

Theoretical Study of Water Cluster Catalyzed Decomposition of

Formic Acid
Satoshi Inaba*,†,‡
†
School of International Liberal Studies, Waseda University, 1-6-1 Nishiwaseda, Shinjuku-ku, Tokyo 169-8050, Japan
‡
Department Terrestrial Magnetism, Carnegie Institution of Washington, 5241 Broad Branch Road NW, Washington, D.C.
20015-1305, United States
*
S Supporting Information
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ABSTRACT: We have performed a number of quantum chemical simulations to examine water

cluster catalyzed decomposition of formic acid. The decomposition of formic acid consists of two
competing pathways, dehydration, and decarboxylation. We use the Gaussian 4 method of the
Gaussian09 software to locate and optimize a transition state of the decomposition reaction and
obtain the activation energy. The decomposition starts by transferring a proton of a formic acid
to a water molecule. The de Broglie wavelength of a proton is similar to the width of the
potential barrier of the decomposition reaction at low temperature. The tunneling, in which a
proton penetrates the potential barrier, enhances the decomposition rate. Water molecules serve
as the catalyst in the decomposition and reduce the activation energy. The relay of a proton from
a water molecule to a neighboring water molecule is accomplished with little change of the
geometry of a molecule, resulting in the reduction of the activation energy. Two water molecules
are actively involved in the decomposition reaction to reduce the activation energy. We have also
examined the effect of water clusters with three, four, and five water molecules on the
decomposition reaction. The noncovalent distance between a hydrogen atom of a water
molecule and an oxygen atom of a neighboring water molecule decreases in a water cluster due to the cooperative many-body
interactions. A water molecule in a water cluster becomes a better proton donor as well as a better proton acceptor. The
activation energy of the decomposition is further decreased by the catalytic effect of a water cluster. We calculate the reaction rate
using the transition state theory corrected by the tunneling effect of a proton. The calculated reaction rate of the decarboxylation
is smaller than that of the dehydration when less than three water molecules are included in the simulation. However, the major
product of the decomposition of a formic acid becomes carbon dioxide and hydrogen molecule formed by the decarboxylation
when a water cluster with more than four water molecules serves as catalyst in the decomposition of formic acid.

■ INTRODUCTION
A water gas shift reaction is one of the important reactions in
of two parallel competitive pathways, decarboxylation and
dehydration:
industry and contains formic acid as an intermediate.1 A carbon cis‐HCOOH → CO2 + H 2 decarboxylation (1)
monoxide reacts with a water molecule to form a carbon
dioxide and a hydrogen molecule. A water gas shift reaction in trans‐HCOOH → CO + H 2O dehydration (2)
supercritical water is a method to produce hydrogen molecules
effectively for fuels.2 It was proposed to use formic acid to store Many experimental results showed that the main pathway of
hydrogen molecules safely for fuel.1 A water gas shift reaction is the decomposition of formic acid in a gas phase is the
a part of a reaction network involving single carbon compounds dehydration, leading to the major product of CO with an order
in subseafloor hydrothermal systems.3 The reaction network of magnitude smaller CO2 yield.4−6 A number of theoretical
generates the energy to support life in the hydrothermal calculations were carried out to find the activation energies for
environments. Reactions involving formic acid are very the decarboxylation and the dehydration in a gas phase.5,7−10
important and were studied extensively by experiment and Similar activation energies for the decarboxylation and the
theory. dehydration were obtained; however, the activation energy for
The decomposition of formic acid in a gas phase diluted in the dehydration is a little smaller than that for the
Ar is described by the molecular elimination processes.4 The decarboxylation. Hu et al.11 examined the effect of H2 formed
decomposition of formic acid to radicals was found to be by the decarboxylation on the decomposition of formic acid.
negligible.4,5 Formic acid has two isomers: trans-HCOOH and They found that the hydrogen molecule opens a new channel
cis-HCOOH. Two hydrogen atoms are on the same side with
respect to the CO bond in a cis-HCOOH, whereas they are on Received: March 1, 2014
the opposite side in a trans-HCOOH. The molecular Revised: April 3, 2014
elimination processes starting from different isomers consist Published: April 15, 2014

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of the dehydration, resulting in the enhancement of the mobility in liquid water, due to the hydrogen bond network.
decomposition of formic acid to CO. In the new channel of the Water dimer, trimer, tetramer, and pentamer were confirmed
dehydration, formic acid reacts with H2 to form formaldehyde using the far-infrared vibrational−rotational-tunneling spectros-
and then it decomposes into CO. copy experiments.24−27 The energy of a water cluster is smaller
Experimental studies showed that the decomposition of than the sum of the energies of the individual water molecules
formic acid in aqueous solution was also described by the by the hydrogen bonds in a water cluster. The covalent bond
molecular elimination processes.12 The decarboxylation be- distance between a hydrogen atom and an oxygen atom in a
comes the main decomposition process in an aqueous solution, water cluster increases while the noncovalent bond distance in a
producing CO2 as the major product of the decomposition, water cluster decreases by the cooperative many-body
whereas the dehydration yields an order of magnitude lower interactions. It is expected to reduce the activation energy of
CO.12 Ruelle et al.13,14 proposed a new mechanism of the the decomposition by the catalytic effect of a water cluster
decomposition of formic acid in which water molecules because the less energy is required to transfer a proton in a
produced as a product of the dehydration serve as catalyst in water cluster. We examine the decomposition of a formic acid
the decomposition for formic acid and reduce the activation catalyzed by water clusters with three, four, and five water
energy of the decomposition. Melius et al.15 performed molecules.

■
quantum chemical simulations with water solvation effect and
found that transition states are stabilized by the water, reducing
the activation energy of the decomposition reaction. Tokmakov COMPUTATIONAL METHODS
et al.16 also studied the water catalyzed decomposition as well We perform a number of quantum chemical simulations with
as the self-catalyzed decomposition process involving the dimer the Gaussian 09 software.22 We use the Gaussian 4 method to
of formic acid. They found the activation energy for the optimize the geometry of a molecule and to calculate the
decomposition of the dimer of formic acid are larger than that vibration frequencies of the molecule. We chose the Gaussian 4
for the water catalyzed decomposition of formic acid. On the method because it was shown that it gives the small error in the
other hand, Wang et al.17 found the smaller activation energy enthalpy of formation by comparing with the 454 experimental
by the dimer of formic acids and implied the catalytic effect of energies (0.83 kcal/mol in average).23 We perform quantum
the dimer of formic acids. The catalytic effect of water chemical simulations of a supermolecule that consists of a
molecules is very important and is included in theoretical formic acid and water molecules.
studies of other reactions as well (e.g., the hydration of carbon We make quantum chemical simulations to obtain the
dioxide18 and the oxidation reaction of ethanol19). electronic energy of a molecule. The thermal correction is
Akiya and Savage20 examined the decomposition of formic added to the electronic energy to obtain the total energy of the
acid with two water molecules, taking into account of the molecule. The thermal correction consists of the corrections
isomers of formic acid. A trans-HCOOH is more stable than a due to the vibration motion of the atomic nuclei, the rotational
cis-HCOOH due to the long distance between hydrogen atoms. motion of the molecule, and the translation motion of the
The isomerization of formic acid proceeds through the internal molecule. The atomic nuclei vibrate in the electric field formed
rotation of the OH bond around the CO bond. They found by the electrons and the atomic nuclei. The vibration
that the activation energy for the isomerization of formic acid is frequencies of the atomic nuclei in the molecule give the
determined independently of water molecules. On the other thermal correction by the vibration.
hand, they obtained the reduced activation energy for the The electronic energy difference of a reactant compound and
decomposition by water molecules. Chen et al.10 increases the a transition state corresponds to the energy barrier of a
number of water molecules included in quantum chemical reaction. A particle is required to overcome the electric
simulations to three water molecules. They used the Gaussian 2 repulsion for a reaction to proceed. The reaction rate is
method in the Gaussian software because the Gaussian 2 dependent on the difference of the electronic energies
method is the most reliable method to obtain the energy of a
corrected by the zero point vibration energy, ΔE0. The
molecule at that time.21 It is necessary to adopt a sophisticated
transition state theory expresses the reaction rate as
method to obtain the accurate activation energy for the
decomposition of a formic acid even though it takes long to q‡ k T
B
perform numerical simulations. Inexpensive methods, on the kclassical = exp( −ΔE0 /kBT )
other hand, have the difficulty to describe the transfer of a qrc h (3)
proton accurately, leading to the incorrect conclusion on the
decomposition of formic acid. They showed that the activation where q‡ and qrc are the partition functions of a transition state
energy is further reduced by the additional third water and a reactant complex, respectively, and kB, T, and h are the
molecule. Boltzmann constant, the temperature, and the Planck constant.
In the present study we apply the Gaussian 4 method of the The partition function factors into a product of the individual
Gaussian09 software22 to locate and optimize the geometry of partition functions due to translation, electric motion, rotational
transition states, reactant compounds, and product compounds motion, and vibrational motion. The reaction rate depends on
of the decomposition reaction. The Gaussian 4 method was the partition functions of the rotational and vibrational motions
shown to give the enthalpy of formation of molecules the most because a reactant complex and a transition state have the same
accurately among available methods.23 We increase the number partition functions of translation and electric motion. The
of water molecules included in a simulation to five and find if rotational partition function is given by
more water molecules can play an important role to reduce the
activation energy. πT 3
A water molecule in a liquid phase tends to have hydrogen qr =
ΘxΘyΘz (4)
bonds with neighboring water molecules. A proton has the high
3027 dx.doi.org/10.1021/jp5021406 | J. Phys. Chem. A 2014, 118, 3026−3038
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where Θx, Θy, and Θz are the rotational temperatures. Assuming where
vibrational modes are independent of each other, we obtain the
vibrational partition function as 2πa = 2 α1ξ (α1−1/2 + α2−1/2)−1 (16)
1
qv = ∏ 2πb = 2 ( −1 + ξ)α1 + α2 (α1−1/2 + α2−1/2)−1 (17)
i
1 − exp( −hνi /kBT ) (5)
where νi is the frequency of the ith vibrational mode. We find 2πd = 4α1α2 − π 2 (18)
the rotational temperatures and the vibrational frequencies in
the output file of the Gaussian 4 and calculate the partition and
functions of a reactant compound and a transition state with E
eqs 4 and 5. ξ=
V1 (19)
A reaction proceeds only when the energy of a particle is
larger than the potential energy barrier in the classical The function cosh (2πd) in eq 15 is replaced by cos(2π|d|) if d
mechanics. However, the quantum mechanics suggests that is imaginary.
even a particle with the energy less than the potential energy Assuming that particles follow the Boltzmann distribution,
barrier is able to penetrate the barrier to ignite a reaction. The the tunneling correction factor, Γ*, is given by
effect referred to as the tunneling effect is crucial to evaluate the ∞
reaction rate.28−30 The potential barrier is well approximated by Γ* = exp(V1/kBT ) ∫0 exp(−E /kBT )κ(E)d(E /kBT )
the unsymmetrical Eckart potential with three parameters, A, B,
and L, and is given by (20)
Ay By We evaluate the above integral numerically to obtain Γ*. The
V=− − reaction rate including the tunneling effect is finally given by
1−y (1 − y)2 (6)
kquantum = Γ*kclassical (21)
y = −exp(2πx /L) (7)
We compare the classical decomposition rate of a formic acid
where L is the half width of the potential barrier. The three with the quantum decomposition rate and show the significant
parameters are determined by the shape of the potential energy tunneling effect at the low temperature.

■
distribution:
A = V1 − V2 (8) NUMERICAL RESULTS
We use the Gaussian 4 method to obtain the optimized
B = ( V1 + V2 )2 (9) geometry of molecules. Figure 1 shows the optimized geometry
of the molecules we consider in this study. The reactants for the
and decomposition of a formic acid are the isomers of a formic acid,
cis-HCOOH, and trans-HCOOH, and the products are four
2 ⎛ 1 1 ⎞−1
L = 2π − ⎜⎜ + ⎟⎟ inorganic molecules, CO2, H2, CO, and H2O. The computer
F * ⎝ V1 V2 ⎠ (10) program, MOLDEN, is used to display the geometry of the
molecules.31
where V1 and V2 are the differences of the potential energies The optimized geometry of the transition states for the
between a transition state and a reactant complex and that decomposition of a cis-HCOOH and a trans-HCOOH is shown
between a transition state and a product complex, respectively, in Figure 1 as well. It is not difficult to identify the pathway for
and F* is the second derivative of the potential energy the decomposition of a formic acid from the geometry of a
evaluated at the transition state. transition state. We could confirm eqs 1 and 2 that the
Rather than the above three parameters, V1, V2, and F*, the decomposition pathways from a cis-HCOOH and a trans-
transmission probability of a particle with mass, m, is expressed HCOOH correspond to the decarboxylation and the
in a simple formula with the following three parameters, u, α1, dehydration, respectively. A transition state for the decom-
and α2: position of a formic acid is found using the synchronous transit
u = hν /kBT (11) guided quasi Newton method. In the Gaussian 09 we choose
the option of qst2 and give tentative structures of reactant and
1 −F * product compounds to locate a transition state. A transition
ν= state is located at a saddle point of the potential energy surface
2π m (12)
and has only one imaginary frequency of vibration. Once a
2πV1 transition state is found, we use the option of IRC to follow the
α1 =
(13)
intrinsic reaction coordinate. By finding reactant and product
hν compounds at both ends of the intrinsic reaction coordinate,
2πV2 we confirm the transition state lies on the intrinsic reaction
α2 = coordinate that actually connects the two energy minimum
hν (14)
points on the potential energy surface. The obtained reactant
The transmission probability of a particle with the energy, E, is and product compounds are optimized further to find the
given by vibration frequencies of the compounds. This last step is
cosh(2π (a + b)) − cosh(2π (a − b)) required because the energy difference of a transition state and
κ (E ) = a reactant compound corresponds approximately to the
cosh(2π(a + b)) + cosh(2πd) (15) activation energy of the decomposition.20
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Figure 1. Optimized geometry of cis-HCOOH, trans-HCOOH, CO2,

H2, CO, H2O, and transition states for the decomposition of a cis- Figure 2. Rate constant for the decomposition of (a) a cis-HCOOH
HCOOH and a trans-HCOOH. TScn and TStn stand for transition (decarboxylation) and (b) a trans-HCOOH (dehydration). The
states for the decomposition of a cis-HCOOH and a trans-HCOOH tunneling effect of a proton enhances the rate constant at low
catalyzed by n water molecules, respectively. The Gaussian 4 method is temperature.
used to obtain the optimized geometry. Gray, brown, and red solid
circles correspond to a hydrogen atom, a carbon atom, and an oxygen
atom, respectively. Atoms with a bond in a molecule are chemically dynamical simulation is not useful to study the formation and
connected with each other. The number near a bond is the bond breaking of molecular bonds. A formic acid and about 2700
length in the unit of angstrom. We add thin solid lines to show the water molecules interact with each other in a box, in which the
distances between atoms in angstrom. temperature and the pressure are regulated to be constant
values, T = 300 K and 1 atm. A three point model of TIP3P is
The classical rate constants, kclassical, for the decomposition of used to describe a water molecule. All the molecules are located
a cis-HCOOH and a trans-HCOOH are calculated using eq 3 as in a box with the side of 48 Å. Periodic boundary conditions
shown in Figure 2a,b. The rate constants increase with an and the particle mesh Ewald method are adopted to include the
increase in the temperature. The energy barrier for the electric forces of molecules outside of the box.
decomposition of a cis-HCOOH is 66 kcal/mol whereas the We make molecular dynamical simulations for 100 ps and
thermal energy of a proton is 0.9 kcal/mol at 25 °C. The huge output the coordinates of all the molecules every 0.01 ps. The
difference of the energies makes the decomposition rate to be a trajectory analysis is carried out with the use of cpptraj in
very small value at the low temperature. The de Broglie AmberTools 13.34 By averaging 10 000 coordinate data of water
wavelength of a proton transferred during the decomposition of molecules, we obtain the radial distribution of water molecules
a formic acid is 1.5 Å at 25 °C, whereas the width of a potential around a formic acid. Figure 3a shows the radial distribution of
barrier for the decomposition of a cis-HCOOH is 1.8 Å. A the number density of water molecules around the carbon atom
proton is able to penetrate the potential barrier without having of a formic acid. The number density is normalized by the
the larger energy than the potential barrier by the tunneling background number density of water molecules. Any water
effect because the de Broglie wavelength is similar to the width molecule cannot approach a formic acid within about 3 Å due
of the potential barrier. We calculate the rate constants, kquantum, to the electric repulsion force by the formic acid. The
for the decomposition of a formic acid by taking into account normalized number density of water molecules increases with
the tunneling effect of a proton, as shown in Figure 2a,b. The the distance from the formic acid and becomes the maximum at
rate constant is enhanced by the tunneling effect at the low 3.5 Å from the formic acid, forming the first hydration shell.
temperature, on the other hand, the tunneling effect does not The second hydration shell seems to appear at 6.3 Å from the
play an important role at the high temperature because the de trans-HCOOH in spite of the small number density. The effect
Broglie wavelength of a proton becomes much shorter than the of a formic acid is reduced with an increase in the distance from
width of the potential barrier. The width of the potential barrier the formic acid and the number density of water molecules
for the decomposition of a trans-HCOOH is wider than that of approaches the background number density. The cumulative
a cis-HCOOH, resulting in the weaker tunneling effect. number of water molecules is shown in Figure 3b. The
It is essential to include interactions of a formic acid with cumulative number of water molecules is the total number of
water molecules to examine the decomposition of a formic acid water molecules that exist within the radius from the carbon
in aqueous solution.32,33 We use Amber 1234 to perform atom of a formic acid. The cumulative number increases rapidly
molecular dynamical simulations to find the distribution of with an increase in the distance from the formic acid. The
water molecules around a formic acid even though a molecular cumulative number of water molecules around a cis-HCOOH is
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at 0 K is smaller than the sum of the total energies of the

individual reactant molecules due to the hydrogen bonds in the
reactant compounds.
The decomposition process starts by transferring a proton
from a formic acid to a water molecule. In the decomposition of
a cis-HCOOH, a proton of the OH bond in a cis-HCOOH
moves to a neighboring water molecule. The excess proton of
the water molecule is transferred to another neighboring water
molecule when two or three water molecules are included in
the simulation. The hydrogen atom with negative charge in the
CH bond of the HCOO and the excess proton in the water
molecule combine to form a hydrogen molecule, leaving CO2,
H2, and water molecules used as the catalyst. All the water
molecules in a ring structure seem to get involved in the
decomposition of a cis-HCOOH; however, IRC calculation
shows that only one water molecule serves as the catalyst in the
decomposition of a cis-HCOOH with four and five water
molecules in a ring structure. Only the water molecule adjacent
to a hydrogen atom of the OH bond in the cis-HCOOH is
involved directly in the decomposition. The water molecule
receives a proton from the OH bond of the cis-HCOOH. The
water molecule with the excess proton rotates with respect to
the hydrogen bond with the next water molecule and transfers
the excess proton to the proximity of a hydrogen atom of the
Figure 3. Radial distribution of (a) the number density of water HCOO to form a hydrogen molecule. The maximum number
molecules normalized by the background number density and (b) the of water molecules involved in the decomposition of a cis-
cumulative number of water molecules around a cis-HCOOH (red) HCOOH in a ring structure is three.
and a trans-HCOOH (green) as a function of the distance from the On the other hand, the decomposition of a trans-HCOOH
carbon atom of a formic acid in angstrom. starts with the transfer of a proton of the CH bond in a trans-
HCOOH to a water molecule. The excess proton of the water
nearly the same as that around a trans-HCOOH. About 15 and molecule moves to a neighboring water molecule and finally
8 water molecules are located within 5 and 4 Å from the carbon attached to the oxygen atom of the OH bond of the COOH.
atom of a formic acid. The decomposition is completed by detaching the newly
The water molecules around a formic acid modifies the formed water molecule from CO. We made several simulations
electric field of the formic acid. It is important to include the with a trans-HCOOH and four water molecules in a ring
interactions of a formic acid and water molecules to study the structure using different initial structures of a supermolecule to
decomposition of a formic acid in aqueous solution. We include examine if more water molecules can be involved in the
water molecules in the simulations as a part of a supermolecule decomposition reaction. We could not find a transition state of
that consists of a formic acid and water molecules because a trans-HCOOH with four water molecules in a ring structure
water molecules are known to serve as catalyst for the and speculate that the maximum number of water molecules
decomposition of a formic acid.10 A proton is transferred involved in the decomposition of a trans-HCOOH in a ring
from a water molecule to another water molecule within a structure is three.
supermolecule.20 We consider a ring structure formed by a Figure 6 shows the optimized geometry of the product
formic acid and water molecules connected with each other by compounds of a cis-HCOOH and a trans-HCOOH with water
hydrogen bonds. The optimized geometry of the transition molecules in ring structures. A hydrogen molecule, a carbon
states for the decomposition of a cis-HCOOH and a trans- dioxide, and a carbon monoxide have nearly the same bond
HCOOH are shown in Figure 4. Up to five and three water length with that shown in Figure 1, indicating that the stable
molecules are included in the decomposition of a cis-HCOOH structure of the molecules are recovered. Clusters of water
and a trans-HCOOH, respectively, because we failed to find a molecules are seen in the product compounds of the cis-
transition state in a ring structure of a formic acid with more HCOOH with four and five water molecules and that of the
water molecules. trans-HCOOH with three water molecules. The total energy of
We follow the intrinsic reaction coordinate from a transition the product compounds is reduced due to the hydrogen bonds
state to obtain the geometry of the reactant and product when water molecules form a water cluster. Square and
compounds. The obtained geometry of the reactant and pentagon structures with nearly the same length of sides are
product compounds is optimized to find the vibration formed by four and five water molecules. A cluster of water
frequencies of the compounds using the Gaussian 4 method. molecules weakly connect with a hydrogen molecule, a carbon
Figure 5 shows the optimized geometry of the reactant dioxide, and a carbon monoxide.
compounds of a cis-HCOOH and a trans-HCOOH with We consider the unimolecular decomposition reaction of a
water molecules in a ring structure. An oxygen atom in a water formic acid from a reactant compound as done by Akiya and
molecule faces a neighboring hydrogen atom, forming a Savage.20 The transition state theory is applied to calculate the
hydrogen bond. The sum of the electrical energy and the classical decomposition rate of a formic acid with eq 3. The
zero point energy of vibration gives the total energy of a classical decomposition rate is corrected by taking into account
supermolecule at 0 K. The total energy of a reactant compound of the tunneling effect of a proton with eq 21. The electrical
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Figure 4. Optimized geometry of transition states for the decomposition of a cis-HCOOH and a trans-HCOOH. Water molecules and a formic acid
form a ring structure. The Gaussian 4 method is used to optimize transition states. Water molecules serve as catalysts of the decomposition and up to
five water molecules are included in the simulations. TScn and TStn stand for transition states for the decomposition of a cis-HCOOH and a trans-
HCOOH catalyzed by n water molecules. We add thin solid lines to show the distances between atoms in angstroms.

energy with the zero point energy shown in Table 1 is one of the major decomposition pathway even though the very small
the most important quantities to determine the decomposition difference of the activation energies is found (1 kcal/mol when
rate. The difference of the energies between a reactant two water molecules are included in the simulations). The
compound and a transition state corresponds to the simulations expect the major products of the decomposition of
approximate activation energy because the ratio of the partition a formic acid in aqueous solution come from the dehydration
function of a reactant compound to that of a transition state and they are CO and H2O when a formic acid and water
weakly depends on the temperature. The approximate molecules form a ring structure. This seems to disagree with the
activation energies for the decarboxylation from a cis- experimental results. However, the major product of the
HCOOH and the dehydration from a trans-HCOOH are decomposition cannot be determined by the activation energy
shown in Figure 7. Both activation energies decrease by about alone. Instead, it is necessary to compare the Gibbs energy of
20 kcal/mol if a water molecule is included in the simulations, the product compounds of the decarboxylation with that of the
indicating the active role of a water molecule as the catalyst. dehydration. The Gibbs energy of the product compounds of
The activation energy for the decomposition of a cis-HCOOH the decarboxylation is always smaller than that of the
becomes smallest, 44 kcal/mol, when two water molecules are dehydration regardless of the number of water molecules
included in the simulation and increases by less than 2 kcal/mol involved in the decomposition, leading the decarboxylation to
if more water molecules are included in the simulation. The the main decomposition path in experiments for long time.
decreasing activation energy for the decomposition of a trans- Water clusters are found in the product complexes in Figure
HCOOH approaches a constant value of 43 kcal/mol when 6. A cluster of water molecules plays a crucial role in the
two water molecules are included in the simulations. The decomposition of a formic acid. Small water clusters with two,
number of water molecules involved in the decomposition of a three, four, and five water molecules were confirmed by the far-
cis-HCOOH and a trans-HCOOH as the effective catalyst is infrared vibrational−rotational-tunneling spectroscopy experi-
two when a formic acid and water molecules form a ring ments.24−27 Figure 8 shows the optimized geometry of small
structure. cyclic water clusters with three, four, and five water molecules35
The activation energy for the decomposition of a cis- obtained with the Gaussian 4 method. One of hydrogen atoms
HCOOH is a little larger than that for the decomposition of a in a water molecule faces an oxygen atom of a neighboring
trans-HCOOH. The smaller activation energy for the water molecule, forming a cyclic network of hydrogen bonds.
decomposition of a trans-HCOOH leads the dehydration to We obtain the larger energy if we consider isomers of the water
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Figure 5. Optimized geometry of reactant compounds for the decomposition of a cis-HCOOH and a trans-HCOOH. The Gaussian 4 method is
used to optimize reactant compounds. Up to five water molecules are included in the simulations as catalysts. RCcn and RCtn stand for reactant
compounds for the decomposition of a cis-HCOOH and a trans-HCOOH catalyzed by n water molecules in a ring structure.

clusters, in which two hydrogens of a water molecule are used water molecules (e.g., a water dimer) also serves as the catalyst
for hydrogen bonds while another water molecule donates no for the decomposition reaction. However, we have already
hydrogen atom for the hydrogen bond in a water cluster. The showed them in Figure 4 and do not repeat them here. We
covalent bond distance between the oxygen and the hydrogen examine the decomposition of a formic acid catalyzed by water
of a water molecule is increased by the hydrogen bond. On the clusters with three, four, and five water molecules. It is seen that
other hand, the noncovalent distance between the oxygen of a a formic acid interacts with two water molecules of the water
water molecule and the hydrogen of a neighboring water cluster in the transition state while the rest of the water
molecule bonded by the hydrogen bond decreases. This molecules are not directly involved in the decomposition
distance further decreases if more water molecules are included process. This can also be interpreted as the following situation.
in a water cluster by the cooperative many-body interactions, as A formic acid is decomposed by the catalyst of the two water
shown in Figure 8. We calculate the bond energy by subtracting molecules in a ring structure that interact with other
the energy of a water cluster from the sum of the energies of background water molecules and have hydrogen bonds.
the individual water molecules: 8.0, 17.3, and 23.9 kcal/mol for We follow the intrinsic reaction coordinate from a transition
the water clusters with three, four, and five water molecules. state and find the geometry of the reactant and product
The energy of each bond for the water clusters with three, four, compounds. We use the Gaussian 4 method to optimize the
and five water molecules are 2.7, 4.3, and 4.8 kcal/mol, geometry of the reactant and product compounds. Figure 10
respectively. A water molecule becomes a better proton donor shows the optimized geometry of the reactant compounds and
as well as a better proton acceptor due to the shorter distance the product compounds. A formic acid attracts a water cluster
of the water molecules in the water cluster. Two water with two hydrogen bonds in a reactant compound. We could
molecules on a side of a water cluster act as the catalyst of the not find a reactant compound of a cis-HCOOH and a water
decomposition, while the rest of water molecules in a water cluster with three water molecules; instead they form a ring
cluster work together to keep the shape of the water cluster. structure. As in the decomposition of a formic acid with water
The optimized geometry of the transition states for the molecules in a ring structure, a proton of the OH bond in a cis-
decomposition of a cis-HCOOH and a trans-HCOOH with HCOOH moves to a neighboring water molecule of a water
water clusters are shown in Figure 9. A water cluster with two cluster, while a proton of the CH bond in a trans-HCOOH is
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Figure 6. Optimized geometry of product compounds for the decomposition of a cis-HCOOH and a trans-HCOOH. The Gaussian 4 method is used
to optimize product compounds. Up to five water molecules are included in the simulations as catalyst. PCcn and PCtn stand for product
compounds for the decomposition of a cis-HCOOH and a trans-HCOOH catalyzed by n water molecules in a ring structure.

Table 1. Relative Electrical Energy Corrected by the Zero Point Energy (kcal/mol) of the Reactant Compounds, the Transition
States, and the Product Compounds with Respect to That of a trans-HCOOH and nH2O for the Decomposition of a Formic
Acid with Water Moleculesa
structure n=0 n=1 n=2 n=3 n=4 n=5
RCcn 3.921 −2.297 −6.480 −17.043 −25.075 −30.914
TScn 70.002 47.996 37.351 29.304 20.749 13.966
PCcn −6.455 −5.427 −10.464 −16.438 −25.166 −32.451
WRCcn −16.970 −21.352 −29.234
WTScn 28.095 19.955 13.145
WPCcn −15.713 −24.937 −32.405
RCtn 0 −1.323 −6.413 −12.527
TStn 67.485 48.807 36.258 30.629
PCtn 3.964 1.060 −4.646 −14.064
WRCtn −11.402 −20.223 −27.344
WTStn 31.352 20.250 12.134
WPCtn −13.354 −20.934 −25.211
a
The relative electrical energy of a cis-HCOOH, CO2 + H2, and CO + H2O with respect to a trans-HCOOH can be found in the reactant compound,
RCc0, the product compound, PCc0, and the product compound, PCt0, respectively. The reactant compounds, the transition states, and the product
compounds of a formic acid with water molecules in a ring structure are denoted by RC, TS, and PC, whereas that with a water cluster are denoted
by WRC, WTS, and WPC. A trans-HCOOH with four and five water molecules in a ring structure is not found because water molecules form a water
cluster.

transferred to a water cluster. The excess proton of the water HCOOH. In the decomposition of a trans-HCOOH, the excess
molecule in a water cluster is transferred to the next water proton is transferred to the oxygen of the OH bond of the
molecule. The excess proton of the water molecule combines
with the hydrogen atom from the CH bond of the HCOO to COOH, forming a water molecule that is moving away from
form a hydrogen molecule in the decomposition of a cis- CO. During the decomposition process, other water molecules
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The Journal of Physical Chemistry A Article

Figure 7. Approximate activation energies for the decomposition of a

cis-HCOOH and a trans-HCOOH when a formic acid and water
molecules form a ring structure. The approximate activation energy is
calculated from the difference of the electrical energies corrected by
the zero point energies between the reactant compound and the
transition state. Up to five and three water molecules are included in
the simulations as catalyst of the decomposition of a cis-HCOOH and
a trans-HCOOH, respectively.

Figure 9. Optimized geometry of transition states for the water cluster

catalyzed decomposition of a cis-HCOOH and a trans-HCOOH. The
Gaussian 4 method is used to locate and optimize transition states.
Water clusters with three, four, and five water molecules are included
in the simulations. WTScn and WTStn stand for transition states for
the decomposition of a cis-HCOOH and a trans-HCOOH catalyzed by
a water cluster with n water molecules, respectively.

Figure 8. Optimized geometry of water clusters with three, four, and

five water molecules. The Gaussian 4 method is used to obtain the molecules in a ring structure is nearly the same as that for the
optimized geometry. decomposition of the formic acid with a water cluster with
three water molecules. With an increase in the number of water
molecules, the activation energy is reduced when a water cluster
keep the hydrogen bonds to maintain the shape of the water is introduced as the catalyst of the decomposition. The lowest
cluster. activation energy becomes 41 kcal/mol when a water cluster
A product compound of the decomposition of a trans- with four water molecules is included in the decomposition of a
HCOOH consists of a carbon monoxide and a water cluster cis-HCOOH. This is about 3 kcal/mol smaller than the smallest
including a water molecule formed by the decomposition. For activation energy obtained when a cis-HCOOH and water
example, the decomposition of a trans-HCOOH catalyzed by a molecules form a ring structure. On the other hand, the
water cluster with five water molecules leaves six water activation energy for the decomposition of a trans-HCOOH
molecules in a book structure. It was shown that a water continues to decrease and becomes the smallest when the
cluster with six water molecules, the water hexamer, have five decomposition of a trans-HCOOH is catalyzed by a water
isomers with nearly the same energies.36 It might be possible to cluster with five water molecules. The activation energy is
find another water cluster form if we adopt a different transition reduced by about 3 kcal/mol by considering the catalytic effect
state. Water clusters are recovered in a product compound and of the water cluster.
act as the catalyst of another decomposition reaction. In the simulations of the decomposition of a cis-HCOOH
The approximate activation energies for the decarboxylation catalyzed by water clusters with four and five water molecules,
and the dehydration are shown in Figure 11 when water all of the four and five water molecules are located within 4 Å
molecules form a water cluster. For comparison the from the carbon atom of a cis-HCOOH. Numerical results of
approximate activation energy is also shown when a formic molecular dynamical simulations show the average number of
acid and water molecules form a ring structure. The activation water molecules within 4 Å from a formic acid is eight as shown
energy for the decomposition of a formic acid with three water in Figure 3b. It might be necessary to include more water
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Figure 10. Optimized geometry of reactant and product compounds for the water cluster catalyzed decomposition of a cis-HCOOH and a trans-
HCOOH. The Gaussian 4 method is used to optimize reactant and product compounds. WRCcn and WRCtn stand for reactant compounds for the
decomposition of a cis-HCOOH and a trans-HCOOH catalyzed by a water cluster with n water molecules, whereas WPCcn and WPCtn stand for
product compounds for the decomposition of a cis-HCOOH and a trans-HCOOH catalyzed by a water cluster with n water molecules.

decrease further if a water cluster with more than six water

molecules is included in the decomposition of a trans-HCOOH.
However, it is beyond the present study to consider the
decomposition of a trans-HCOOH catalyzed by a water cluster
with six water molecules. It was shown that a water cluster with
six water molecules has five isomers with nearly the same
energies.36 It requires large amount of time to examine the
decomposition of a formic acid catalyzed by the five isomers of
the water clusters.
Parts a and b of Figure 12 show the rate constants for the
decomposition of (a) a cis-HCOOH and (b) a trans-HCOOH
catalyzed by up to five water molecules as a function of the
Figure 11. Same as Figure 7 but the activation energy of the temperature. The rate constant of the decomposition of a
decomposition of a formic acid catalyzed by water clusters. Water formic acid catalyzed by a water cluster is shown when more
clusters with three, four, and five water molecules are considered. than three water molecules are included in the simulations
because a water cluster decomposes a formic acid more
molecules in the simulations to find the maximum decom- effectively than water molecules in a ring structure. Both rate
position rate. However, the activation energy for the constants for the decomposition of a cis-HCOOH and a trans-
decomposition of a cis-HCOOH catalyzed by a water cluster HCOOH increase with an increase in the temperature
with four water molecules is smaller than that with five water regardless of the number of water molecules included in the
molecules by 1 kcal/mol. On the other hand, the activation simulations. The rate constant is enhanced by the catalytic
energy for the decomposition of a trans-HCOOH catalyzed by effect of water molecules when a water molecule is introduced
a water cluster with five water molecules becomes smaller than in the simulations. Figure 12a shows that the rate constant
that with four water molecules. The activation energy might increases with an increase in the number of water molecules
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The Journal of Physical Chemistry A Article

interactions between a formic acid and water molecules to

examine the decomposition of a formic acid in aqueous
solution.
We consider a supermolecule that consists of a formic acid
and water molecules. We use quantum chemical simulations to
describe the breaking and formation of bonds between atoms in
the supermolecule. We use the synchronous transit guided quisi
Newton method in the Gaussian09 to locate a transition state
of the decomposition. The approximate activation energy of the
decomposition is obtained from the difference of the electrical
energies corrected by the zero point energies between the
reactant compound and the transition state. The activation
energy is used to calculate the classical decomposition rate of a
formic acid with the transition state theory. It is required to
include the tunneling effect of a proton to obtain the quantum
decomposition rate. The transfer of a proton is the most
important process in the decomposition of a formic acid and
needs to be treated very accurately. Even a proton with the
energy less than the activation energy for the decomposition
can penetrate the potential barrier to ignite the decomposition
process by the tunneling. The de Broglie wavelength of a
proton becomes long at the low temperature, increasing the
tunneling correction factor for the decomposition. However,
Figure 12. Rate constant for the decomposition of (a) a cis-HCOOH the tunneling effect on the decomposition becomes weak at the
(decarboxylation) and (b) a trans-HCOOH (dehydration) catalyzed high temperature due to the short de Broglie wavelength
by water clusters with three, four, and five water molecules and water compared with the width of the potential barrier.
molecules in a ring structure. The decomposition is catalyzed by one
We also found that the activation energy for the
and two water molecules that form a ring structure with a formic acid.
A formic acid is decomposed more effectively by a water cluster when decomposition of a formic acid is significantly reduced by
more than three water molecules are included in the simulation. water molecules included in the simulations. The decom-
position process starts by the transfer of a proton in a formic
acid to a water molecule. The excess proton of the water
and approaches the maximum value when water clusters with
molecule is transferred to a neighboring water molecule bonded
four and five water molecules are available for the
by the hydrogen bond. The excess proton from the water
decomposition of a cis-HCOOH. On the other hand, the little
increase in the rate constant is found when more than two molecule combines with the hydrogen atom of the CH bond in
water molecules are included in the decomposition of a trans- a cis-HCOOH to form a hydrogen molecule in the
HCOOH as shown in Figure 12b. Figure 11 shows that the decarboxylation, while the excess proton is captured by the
activation energy for the decomposition of a trans-HCOOH oxygen atom of the OH bond in a trans-HCOOH to form a
decreases with the increasing number of water molecules. carbon monoxide and an extra water molecule in the
However, the ratio of the partition function of a transition state dehydration. Two water molecules serve as the catalyst most
to that of a reactant compound decreases and offsets the effectively in the decomposition when a formic acid and water
decreased activation energy. molecules form a ring structure.

■
The rate constant is further increased if we consider the
SUMMARY decomposition of a formic acid catalyzed by a water cluster.
We studied the decomposition of a formic acid catalyzed by The noncovalent distance between the oxygen of a water
water clusters with three, four, and five water molecules as well molecule and the hydrogen of a neighboring water molecule
as water molecules in a ring structure. We made a number of bonded by the hydrogen bond in a water cluster becomes short
quantum chemical simulations using the Gaussian 4 method in by the cooperative many-body interactions. Water molecules in
the Gaussian09 software to locate and optimize the geometry of a water cluster becomes a better proton donor as well as a
transition states, reactant compounds, and product compounds. better proton acceptor. Two water molecules of a water cluster
The Gaussin 4 method is known to have the least errors when act as the catalyst in the decomposition while the other water
we calculate the enthalpy of formation for molecules. molecules keep the shape of the water cluster by the hydrogen
A formic acid decomposes in two competitive pathways: bonds. A water cluster plays a significant role in the
decarboxylation and dehydration. A formic acid in aqueous decomposition of a formic acid.
solution decomposes mainly into CO2 and H2 by the The rate constant for the decarboxylation is larger than that
decarboxylation with a small amount of CO and H2O by the for the dehydration when a water cluster serves as catalyst of
dehydration. We made molecular dynamical simulations using the decomposition, leading the decarboxylation to the main
the Amber 12 software to find the distribution of water decomposition pathway. We also found that the Gibbs energy
molecules around a formic acid. The radial distribution of water of the product compound from the decarboxylation, CO2 and
molecules is modified by a formic acid, showing the first H2 with water molecules, is always smaller than that from the
hydration shell at 3.5 Å from the carbon atom of the formic dehydration, CO and H2O with water molecules. The main
acid. The average number of water molecules within 4 Å from decomposition products are expected to be CO2 and H2, from
the formic acid is about eight. It is crucial to include the the decarboxylation and agree with experiments.
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The Journal of Physical Chemistry A Article

Some experiments showed that the decomposition of a Comparison of the Gas-Phase and Aqueous-Phase Results. J. Phys.
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acid in an acidic condition.

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Chemical Study of the Unimolecular Pyrolysis Mechanisms of Formic
Acid. J. Am. Chem. Soc. 1986, 108, 371−375.
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*
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Table of the rate constants (1/s) for the decomposition of a cis- (15) Melius, C. F.; Bergan, N. E.; Shepherd, J. E. Effects of Water on
HCOOH and a trans-HCOOH catalyzed by n water molecules Combustion Kinetics at High Pressure. 23rd Symposium (International)
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material is available free of charge via the Internet at http:// (16) Tokmakov, I. V.; Hsu, C.-C.; Moskaleva, L. V.; Lin, M. C.
pubs.acs.org. Thermal Decomposition of Formic Acid in the Gas Phase:

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Bimolecular and H2O Catalysed Reactions. Mol. Phys. 1997, 92,
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(17) Wang, B.; Hou, H.; Gu, Y. New Mechanism for the Catalyzed
Corresponding Author Thermal Decomposition of Formic Acid. J. Phys. Chem. A 2000, 104,
*E-mail: satoshi.inaba@waseda.jp. Phone: 81-3-5286-1730. 10526−10528.
Notes (18) Nguyen, M. T.; Raspoet, G.; Vanquichenborne, L. G.; Duijnen,
The authors declare no competing financial interest. P. T. V. How Many Water Molecules Are Actively Involved in the

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Neutral Hydration of Carbon Dioxide? J. Phys. Chem. A 1997, 101,
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We performed most of the computations in Research Center Reactions Catalyzed by Water Molecules: CH3CH2OH + n H2O →
for Computational Science, Okazaki, Japan. We acknowledge CH3CHO + H2 + n H2O (n = 0,1,2). Chem. Phys. Lett. 2002, 363, 80−
Shohei Ohara for helpful discussions. We also express our 86.
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Department of Terrestrial Magnetism at the Carnegie
(21) Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Pople, J. A.
Institution of Washington during the 2013−2014 sabbatical Assessment of Gaussian-2 and Density Functional Theories for the
year in the U.S.A.

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Computation of Enthalpies of Formation. J. Chem. Phys. 1997, 106,
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