RESEARCH ARTICLE | JANUARY 15 1992

The decarboxylation and dehydration reactions of

monomeric formic acid 
John D. Goddard; Yukio Yamaguchi; Henry F. Schaefer, III

J. Chem. Phys. 96, 1158–1166 (1992)

https://doi.org/10.1063/1.462203

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17 August 2023 20:14:11

The decarboxylation and dehydration reactions of monomeric formic acid
John D. Goddard,a) Yukio Yamaguchi, and Henry F. Schaefer III
Center/or Computational Quantum Chemistry, University o/Georgia, Athens, Georgia 30602
(Received 11 July 1991; accepted 30 September 1991)
Two unimolecular dissociation reactions offormic acid have been investigated theoretically.
The decarboxylation reaction yields molecular hydrogen and carbon dioxide, while the
dehydration reaction produces water and carbon monoxide. The 1,2-hydrogen shift
rearrangement from formic acid to dihydroxymethylene has also been considered. Methods
ranged from double zeta plus polarization self-consistent field to triple zeta plus double
polarization coupled cluster singles and doubles. For certain key structures, the coupled cluster
method including single, double, and linearized triple excitations (CCSDT-1) was applied as
well with the double zeta plus polarization basis set. A barrier height of - 71 kcal mol- I with
zero point vibrational energy correction is predicted for the dissociation to molecular hydrogen
and carbon dioxide. A rather comparable value of - 68 kcal mol - I is predicted for the barrier
to the dehydration reaction. The 1,2-hydrogen shift transition state is somewhat higher in
energy at - 79 kcal mol - I. These predicted energy barriers are discussed with reference to the
existing experimental results on the thermal decomposition of formic acid.

INTRODUCTION lation reaction was minor with the ratio of CO to CO 2 being

The dissociation of formaldehyde to molecular hydro-
gen and carbon monoxide has been studied thoroughly both
byexperimene and theory.2 The analogous decomposition
of formyl fluoride to hydrogen fluoride and carbon monox-
approximately 10. This reaction was first order over the
whole range of temperatures (457-780 °C) and an Arrhen-
ius activation energy of 48.5 kcal mol - 1was deduced. Hsu et
al.1O studied the thermal decomposition of formic acid at

17 August 2023 20:14:11

ide has been the object of recent high level theoretical
work. 3,4 The unimolecular decompositions of acetaldehyde
either to methane and carbon monoxide or to ketene and
molecular hydrogen have also been examined theoretically
in very recent studies. 5.6 All these reactions involve mole-
cules containing the formyl group, HCO, dissociating into
molecular products. Formic acid, a formyl group containing
organic compound, presents itself as a natural candidate for
a high level theoretical study of its molecular reactivity, as it
is an important intermediate in the oxidation of unsaturated
hydrocarbons in combustion and in atmospheric chemistry.
In addition, formic acid, like acetaldehyde, has the intrigu-
ing feature of two potentially competing molecular dissocia-
tion pathways:
HCOOH ..... H2 + CO2 decarboxylation, ( 1)
HCOOH ..... H 20 + CO dehydration. (2)
Although there has been revived interest in the electronic
spectroscopy7 and photochemical reactivity8 of formic acid,
the thermal gas phase reactions on the ground state (singlet)
surface of this prototypical carboxylic acid have not been
reexamined recently.
An early experimental study9 on the thermal decompo-
sition of gaseous formic acid established that the only prod-
ucts were H 20, H 2, CO, and CO 2, apparently from both
reactions (1) and (2). At lower temperatures the dehydra-
tion reaction was second order while at higher temperatures
the order was 1.5. Taking the higher temperature dehydra-
tion reaction to be unimolecular, an Arrhenius activation
energy of 60.5 kcal mol - 1 was determined. The decarboxy-
a) Permanent address: Department of Chemistry and Biochemistry, Uni-
versity of Guelph, Guelph, Ontario NIG 2Wl Canada.
1158 J. Chern. Phys. 96 (2), 15 January 1992 0021-9606/92/021158-09$06.00
high temperatures, 1280 to 2030 K, in shock waves. Their
results were explained in terms of the two molecular reac-
tions, dehydration and decarboxylation, and thermochemi-
cal data was used to rule out free radical decompositions.
The A factors reported by Blake et al. 9 in their Arrhenius
analyses were brought into question. Hsu et al. 10 carried out
a two channel RRKM calculation II for dehydration and
decarboxylation and found threshold energies of 62 to 65
kcal mol - 1for dehydration and 65 to 68 kcal mol - 1for de-
carboxylation. As dehydration was the dominant process,
the similar activation energies were commented on by Saito
et al. 12 They examined the thermal decomposition of formic
acid in shock waves in the temperature range 1370 to 2000
K. The decomposition to CO + H 20 was dominant with the
contribution of the channel leading to H2 + CO 2 very small.
Saito et al. 12 presented thermochemical data to indicate the
improbability of free radical processes. Preliminary ab initio
computations by these workers indicated that the decarbox-
ylation barrier was 81.6 kcal mol - 1and the dehydration one
- 62.1 kcal mol - 1. However, later theoretical work (vide
infra) has not supported this large difference in barrier
heights for these two molecular processes.
Several experiments 13-15 employing lasers to initiate the
decomposition offormic acid have been reported. Samsonov
et al. 13 studied the decomposition of formic acid induced by
laser heating and determined Arrhenius activation energies
in the range from 61. 7 to 66.0 kcal mol - 1 for the dehydra-
tion reaction. Multiphoton dissociation of formic acid using
a pulsed HF laser has been examined by two groups. 14.15
Corkum et al. 14 suggested that the decomposition to CO and
H 20 proceeded through a bimolecular reaction between vi-
brationally excited formic acid monomers:
2HCOOH* .... [HCOOH]! .... 2CO + 2H 20.
© 1992 American Institute of Physics
 Goddard, Yamaguchi, and Schaefer III: Reactions of monomeric formic acid 1159

Many theoretical studies have been published on the were obtained analytically at the SCF level and by the finite
structures of cis- and trans-formic acid and on the internal difference method at the correlated level.
rotation barrier between these two conformations, e.g., Refs. The effects of higher levels of theory on the predicted
16 to 18. A thorough theoretical examination of the vibra- energy differences were examined in two ways. CCSD theo-
tional spectra of both monomeric and dimeric formic acid ry was applied with the larger TZ + 2P basis to assess basis
has been reported. 19 Ab initio studies of the 1,2-hydrogen set extension effects. The CCSDT-1 approach which includ-
shift rearrangement from formic acid to dihydroxymethy- ed single, double and linearized triple excitations was em-
lene and the complex rotational potential energy surfaces of ployed with the DZ + P basis to examine higher order elec-
the carbene species have appeared. 20,21 Feller et al. 21 indi- tron correlation effects.
cate that the barrier to the 1,2-hydrogen shift from trans-
formic acid to the dihydroxymethylene is on the order of 80 RESULTS AND DISCUSSION
kcal mol-I. Molecular structures
The theoretical studies most relevant to the molecular
The predicted geometries for cis- and trans-formic acid
decompositions of formic acid were by Ruelle and co-
at three levels of theory are given in Fig. 1. The designation
workers. 22 ,23 Ruelle predicted23 by MP4SDTQ/6-31 G**
of cis-formic acid matches that of the original experimental
single point energy calculations at MP2I6-31G** opti-
work 33 on this species, i.e., the hydrogens are cis. The experi-
mized geometries that the classical (i.e., no corrections for
mental structures given in parentheses in the figure are taken
zero point vibrational energies) barriers were 7S.97
from Refs. 32 to 35. These structural predictions are sensi-
kcal mol- I for decarboxylation and 78.7 kcal mol- 1 for de-
tive to the balance between the size and type of basis set and
hydration. The similarity in these barrier heights in contrast
the level of inclusion of electron correlation effects. All the
to the product ratio of CO to CO 2 of 10 to 1 lead Ruelle to
DZ + P SCF bond lengths are slightly shorter than the ex-
postulate that the decarboxylation reaction proceeded by a
perimental values. The inclusion of electron correlation at
more complicated water catalyzed bimolecular reaction.
In the present study we have reinvestigated the decar-
boxylation and dehydration reactions of formic acid with
larger basis sets and with the more complete incorporation

17 August 2023 20:14:11

of electron correlation through coupled cluster approaches. o
H
The 1,2-hydrogen shift transition state has been considered
to further explore the possible involvement of dihydroxy-
methylene in the thermal reactivity of formic acid.

COMPUTATIONAL METHODS 111.4·

cis - Fonnic Acid
109.4·
The basis sets used were of double zeta plus polarization 108.7·
(~I09.7")0
(DZ + P) type or larger. The standard Huzinaga-Dun-
ning 24 ,2S double zeta Gaussian basis sets were employed. H
0.947
0.961
Thus the DZ + P basis consists of C,O (9sSpld /4s2pld) 0.968
(0.9S6)
and H (4s1p/2s1p). The hydrogen s functions were scaled
by 1.2. Polarization function exponents were ad (C) = 0.75,
ad (0) = 0.8S, and a p (H) = 0.7S. A triple zeta plus double
polarization (TZ + 2P) basis set2 6 was used in certain of the
computations. This TZ + 2P basis set can be denoted C,O o H
(9sSp2d /Ss3pld) and H (4s2p/3s2p) and is triple zeta in the
valence shell. The polarization function orbital exponents
were ad(C) = 1.500, 0.375; ad(O) = 1.700, 0.425; and
a p (H) = I.S00, 0.375 for this TZ + 2P basis set. 1.324
1.341
Geometries were optimized using analytic gradient 1.3S1 trans - Fonnie Acid
106.6· (1.343)
techniques 27 - 29 at the self-consistent field (SCF) level and (106.3") 0
with the configuration interaction with single and double
excitations (CISD) method. For selected structures, cou-
DZ+PSCF
H~ 0.96S
0.973
pled cluster singles and doubles (CCSD) 30,31 geometryopti- DZ+PCISD (0.972)
mizations were carried out. In determining the CISD geo- DZ+PCCSD
metries, three core orbitals were frozen and three virtual (Experiment)
orbitals deleted. Any CCSD geometry optimizations in-
volved all electrons and all orbitals. SCF and CISD harmon-
ic vibrational frequencies were evaluated to unambiguously FIG. I. Predicted structures for trans- and cis-formic acid. Geometries were
determined at the double zeta plus polarization (DZ + P) self-consistent
characterize stationary point structures and to provide the field (SCF) level, at the DZ + P configuration interaction with single and
necessary data to compute zero point vibrational energy cor- double excitations (CISD) level and at the DZ + P coupled cluster singles
rections to predicted energy differences. These frequencies and doubles (CCSD) level. Experimental results are shown in parentheses.

J. Chem. Phys., Vol. 96, No.2, 15 January 1992

1160 Goddard, Yamaguchi, and Schaefer III: Reactions of monomeric formic acid

the DZ + P CISD level leads to a lengthening of all bond 1.151 o

1.170
distances and an improvement in the agreement with experi- 1.179
ment. Proceeding to the more highly correlated CCSD
H-----,,....
method with the same DZ + P basis set, all bond distances 148.80
148.30
become slightly greater than the experimental values. The 148.0"
Decarboxylation
average signed deviations of all predicted bond lengths in the 1.020 \
1.005 \
Transition State
two conformers from experiment are highly satisfactory: 1.009 \
- 0.Q15 DZ + P SCF, - 0.002 DZ + P CISD, and H
+ 0.006 DZ + P CCSD.
With a single exception the changes in bond angles with
level of theory are less than 1°. The exception is the COH
DZ+PSCF
angle in both cis- and trans-formic acid. In the cis-isomer, the DZ+PCISD
COH angle decreases from 111.4° at the SCF level to 109.4° DZ+PCCSD
and 108.7° with the CISD and CCSD approaches. The equiv-
alent angle in trans-formic acid changes from 109.0° DZ + P FIG. 3. The predicted structure for the decarboxylation transition state
SCF to 107.2° DZ + P CISD and to 106.6° DZ + P CCSD. connecting the reactant, cis-fonnic acid, with the products, molecular hy-
A change of such a magnitude in XOH angles with the inclu- drogen and carbon dioxide. Geometries were detennined at the double zeta
sion of electron correlation has been observed previously for plus polarization (DZ + P) self-consistent field (SCF), at the DZ + Pcon-
figuration interaction with single and double excitations (CISD), and at the
molecules such as CH 30H and NH 20H (e.g., Ref. 36, Ta- DZ + P-coupled cluster singles and doubles (CCSD) levels.
ble 6.7).
The transition state for the internal rotation connecting
trans- to cis-formic acid proved interesting as its precise loca-
and all the three levels of theory agree qualitatively on its
tion by geometry optimization techniques was an unexpect-
features. The decarboxylation transition state is most readily
ed challenge. Theoretical predictions at SCF and CISD lev-
visualized as arising from the cis conformation. The hydro-
els for this transition state are shown in Fig. 2. Note that the
gens which will form the H2 molecule are slightly more than
HCOO fragment is not exactly planar. The dihedral angles
1.0 A apart. The hydrogen breaking away from oxygen is at
at the transition state are close to 90° (95.8° SCF, 95.2°

17 August 2023 20:14:11

1.268 to 1.308 A which represents an ~0.3 A increase rela-
CISD) as would be expected, given that the trans- and cis-
tive to cis-formic acid. The CH bond is stretched to ~ 1.43 A
forms are quite close (vide infra) in energy. The CO bond
in this transition state and the HCO and OCH angles are
about which the rotation occurs lengthens by ~0.02 A in the
quite small at 98° to 99° and 69° to 67°, respectively. Thus a
transition state as conjugative effects between the 0 lone
rather tight four center, HCOH, transition state structure
pairs and the carbonyl group are minimized. This CO bond
results. The OCO angle which will be 180° in the carbon
length still remains shorter than a usual single bond.
dioxide product is ~ 148° in the transition state. One CO
The optimized geometries for the four-center transition
bond length is 1.15 to 1.17 A and thus close to the value 32 in
state of the decarboxylation reaction are shown in Fig. 3 at
CO 2 of 1.160 A. The other CO distance is 1.238 to 1.265 A
three levels of theory. This transition state structure is planar
depending on the level of theory. The HH bond and one CO
bond which are forming are significantly longer than their
equilibrium distances in the products. Some vibrational exci-
tation of the H2 and CO 2 products might be inferred. This
o decarboxylation transition state is fairly similar to that
1.178 found at the UMP2/6-31G** level by Ruelle z3 and with
UMP2/6-311 G* by Francisco. 37
1.195

124.0" The dehydration transition state (see Fig. 4) differs

Internal
from that determined by Ruelle and co-workers 22.23 as it is
123.9°
Rotation
Transition State significantly nonplanar. It would appear that the transition
state reported earlier by Ruelle zz •z3 was not a true first order
saddle point but rather second order, with an out-of-plane
bending imaginary frequency as well as the frequency corre-
sponding to the reaction coordinate. A similar conclusion
t (OCOH,) 95.80
95.20 has been drawn by Francisco. 37 This dehydration transition
state is formed directly from the trans-isomer. In Fig. 4 the C
to 0 bond which is cleaving as Hz 0 is formed is quite long at
DZ+PSCF
DZ+PCISD 1.85 ASCF or 1.82 A CISD. The OH[ distance and the CO
distance in the forming carbon monoxide are both quite
close to product equilibrium values. The hydrogen which is
FIG. 2. The predicted geometry for the internal rotation transition state shifting is ~ 1.15 to 1.16 A from C and ~ 1.3 9 to 1.3 8 A from
structure between trans- and cis-fonnic acid. This structure was detennined
at the double zeta plus polarization (DZ + P) self-consistent field (SCF)
o and is ~ 7° to 10° out of the OCO plane. The present ver-
and at the DZ + P configuration interaction with single and double excita- sion of the CCSD gradient programs did not allow the reop-
tions (CISD) levels. Note that the HCOO fragment is not exactly planar. timization of this nonplanar transition state at the

J. Chem. Phys., Vol. 96, No.2, 15 January 1992

 Goddard, Yamaguchi, and Schaefer III: Reactions of monomeric formic acid 1161

o characteristic tight bridge as it is 1.214 or 1.235 A. from e

Dehydration and a similar distance of 1.220 to 1.233 A. from O. This HOC
Transition State
angle is close to 60· and the CO across which the shift takes
place is 1.265 to 1.300 A. in length. The other CO bond is

/:'
beginning to show partial multiple bond character as antici-
1.854 pated for the carbene as it shortens by ~ 0.03 A. from the
1.818
value in formic acid.
/ U~9
,/ Classical barrier heights
58.8·
t (OCOH2l 173.7·
Tables I through V present the total energies in hartree
170.5· and the relative energies in kcal mol - 1 with respect to trans-
formic acid for the minima and transition states examined in
DZ+PSCF
DZ+PCISD this work. In this section, the classical energy differences and
barrier heights, i.e., without corrections for zero point vibra-
FIG. 4. The predicted structure for the dehydration transition state con-
tional energies, will be considered briefly. Comparisons with
necting the reactant, trans-formic acid, with the products, water and carbon earlier theoretical work and/or experiment will be post-
monoxide. This geometry was predicted at the double zeta plus polarization poned until after the discussion of harmonic vibrational fre-
(DZ + P) self-consistent field (SCF) and DZ + P configuration interac- quencies in the next section.
tion with single and double excitations (CISD) levels. Note that this transi-
tion state geometry is non planar.
Table I contains the theoretical predictions of this work
for the energy difference between trans- and cis-formic acid.
The barrier height for the internal rotation between trans-
and cis-formic acid is predicted in Table II. Tables III and IV
DZ + P eeSD level of theory due to computer limitations. contain the energetic data for the decarboxylation and dehy-
Study of the changes in geometry from DZ + P elSD to dration reactions respectively. Table V presents the energies
DZ + P eeSD for the decarboxylation transition state (re- and barrier heights for the isomerization of formic acid to

17 August 2023 20:14:11

call Fig. 3) suggests the reliability of the DZ + P eISD ge- dihydroxymethylene.
ometry for use in various higher level single point energy The trans isomer is predicted to be more stable at all
calculations. levels of theory. The DZ + P SeF energy difference is 5.67
Figure 5 illustrates the 1,2-hydrogen shift transition kcal mol- 1 which decreased with the inclusion of electron
state connecting trans-formic acid to dihydroxymethylene correlation effects to 5.35 kcal mol-I (DZ + P eISD) or
(the "s conformer" in the notation of Feller et al. 20,21 ) at the 5.20kcal mol-I (DZ + P eeSD). A higherlevel treatment
DZ + P SeF, DZ + P eISD, and DZ + P eeSD levels. of electron correlation, eeSDT-l, with the same DZ + P
This transition state is also formed directly from trans-for- basis set does not change this energy difference to one deci-
mic acid. The hydrogen undergoing the 1,2-shift shows the mal place. However, there is a significant decrease in the
trans to cis energy difference with extension of the basis set to
TZ + 2P and use of the CeSD approach. The' TZ + 2P
1.220
eCSD energy difference in this work is 4.47 kcal mol - 1
1.225 which is fortuitously rather similar to the MP3/6-
I..:~~........ H
311 + G** result of 4.61 kcal mol- 1 found by Wiberg and
0"
Laidig. I7 Measured relative to the more stable trans isomer
58.S"
58.3·
58.3°
the rotational barrier previously has been predicted to be
1,2 - Hydrogen Shift ~ 12 kcal mol- 1, e.g., Refs. 16 and 17. The DZ + P seF
Isomerization classical barrier height in Table II is 12.69 kcal mol- 1 which
Transition State
increases at the DZ + P eISD level to 13.14 kcal mol- 1.
1.297
1.313
The more complete eeSD and eeSDT-1 treatments of elec-
1.323 tron correlation also predict slight increases in the barrier
relative to SeF results to 12.98 and 13.37 kcal mol- 1, re-
spectively. The effects of basis set extension were not evalu-
H ated explicitly for the internal rotation transition state and
could change the barrier by approximately 10% or ~ 1.0 to
1.5 kcal mol - 1. This relatively large barrier height for an
DZ+PSCF
DZ+PCISD internal rotation indicates that the e-O bond has some mul-
DZ+PCCSD tiple bond character.
Turning to the decarboxylation reaction, the classical
FIG. 5. The predicted structure for the 1,2·hydrogen shift isomerization barrier height from the DZ + P eeSD method at the consis-
reaction connecting trans-formic acid to dihydroxymethylene. This geome-
tent DZ + P eeSD optimized geometry is predicted to be
try was predicted at the double zeta plus polarization (DZ + P) self-consis-
tent field (SCF) and DZ + P configuration interaction with single and dou- 80.89 kcal mol- 1. Higher level correlation effects included
ble excitations (CISD) levels. with the DZ + P CCSDT-1 modellower the barrier height
J. Chem. Phys., Vol. 96, No.2, 15 January 1992
1162 Goddard, Yamaguchi, and Schaefer III: Reactions of monomeric formic acid

TABLE I. Theoretical energy predictions for the relative stability of trans- and cis-formic acid.

trans-formic acid cIS-formic acid

Energy/ / geometry" E (a.u.) E (a.u.) AE (kcal mol- I)

DZ + P SCF//DZ + P SCF - 188.81444 - 188.80540 5.67

DZ + P CISDb/ /DZ + P CISD - 189.25909 - 189.25056 5.35
DZ + P CCSDb/ /DZ + P CISD - 189.310 96 - 189.30264 5.22
DZ + P CCSDT-I b/ /DZ + P CISD - 189.327 19 - 189.31888 5.21
TZ + 2P CCSDb/ /DZ + P CISD - 189.40571 - 189.39858 4.47
DZ + P CCSD//DZ + P CCSD - 189.35649 - 189.34820 5.20
DZ + P CCSDT-lb //DZ + P CCSD - 189.32783 - 189.31953 5.21
TZ + 2P CCSDb/ /DZ + P CCSD - 189.40537 - 189.39824 4.47

• All CISD wave functions employed three frozen core and three deleted virtual orbitals. DZ + P CCSD geom-
etry optimizations included all orbitals. Single point DZ + P CCSD, DZ + P CCSDT-1 and TZ + 2P CCSD
wave functions used three frozen core and three deleted virtual orbitals.
bThree frozen core and three deleted virtual orbitals.

TABLE II. Theoretical energy predictions for the barrier height to internal rotation from trans-formic acid to
cIS-formic acid. This barrier is reported relative to the more stable trans isomer.

Internal rotation
transition state Barrier height
Energy/ / geometry" E (a.u.) AE (kcal mol- I)

DZ+ PSCF//DZ+ PSCF - 188.79421 12.69

DZ + P CISDb/ /DZ + P CISD - 189.238 15 13.14
DZ + P CCSDb/ /DZ + P CISD - 189.29027 12.98
DZ + P CCSDT-lb / /DZ + P CISD - 189.30589 13.37

• All CISD wave functions employed three frozen core and three deleted virtual orbitals. The DZ + P CCSD

17 August 2023 20:14:11

and DZ + P CCSDT-l results reported in this table also excluded three core and three virtual orbitals.
bThree frozen core and three deleted virtual orbitals.

TABLE III. Theoretical energy predictions for the barrier height for the decarboxylation reaction converting
cis-formic acid to molecular hydrogen and carbon dioxide. This barrier is reported relative to the more stable
trans isomer.

Decarboxylation
transition state Barrier height
Energy//geometrya E (a.u.) AE (kcal mol- I)

DZ + P SCF//DZ + P SCF - 188.66356 94.68

DZ + P CISD b/ /DZ + P CISD - 189.12434 84.56
DZ + P CCSD b/ /DZ + P CISD -189.18221 80.79
DZ + P CCSDT-lb / /DZ + P CISD - 189.20522 76.54
TZ + 2P CCSDb/ /DZ + P CISD - 189.277 50 80.45
DZ + P CCSD//DZ + P CCSD - 189.22759 80.89
DZ + P CCSDT -1 b/ /DZ + P CCSD - 189.206 17 76.34
TZ + 2P CCSDb/ /DZ + P CCSD - 189.277 21 80.42

aAll CISD wave functions employed three frozen core and three deleted virtual orbitals. DZ + P CCSD geom-
etry optimizations included all orbitals. Single point DZ + P CCSD, DZ + P CCSDT-1 and TZ + 2P CCSD
wave functions used three frozen core and three deleted virtual orbitals.
bThree frozen core and three deleted virtual orbitals.
TABLE IV. Theoretical energy predictions for the barrier height for the dehydration reaction converting
trans-formic acid to water and carbon monoxide. This barrier is reported relative to the more stable trans
isomer.

Dehydration
transition state Barrier height
Energy//geometry" E(a.u.) AE (kcal mo1- I)

DZ + P SCF/ /DZ + P SCF - 188.67028 90.46

DZ + P CISD b / /DZ + P CISD - 189.12788 82.34
DZ + P CCSD b/ /DZ + P CISD - 189.18678 77.92
DZ + P CCSDT -1 b/ /DZ + P CISD - 189.20973 73.71

" All CISD wave functions employed three frozen core and three deleted virtual orbitals. The DZ + P CCSD
and DZ + P CCSDT-1 results reported in this table also excluded three core and three deleted virtual orbitals.
bThree frozen core and three deleted virtual orbitals.

J. Chem. Phys., Vol. 96, No.2, 15 January 1992

 Goddard. Yamaguchi. and Schaefer III: Reactions of monomeric formic acid
TABLE V. Theoretical energy predictions for the barrier height for the isomerization of formic acid to dihy-
droxymethylene. This barrier is reported relative to the more stable trans-formic acid.
Isomerization
transition state
Energy//geometry" E (a.u.)
DZ + P SCFIIDZ + P SCF - 188.66490
DZ + P CISD b IIDZ + P CISD - 189.121 84
DZ + P CCSD b / /DZ + P CISD - 189.17930
DZ + P CCSDT-lb I/DZ + P CISD - 189.19969
TZ + 2P CCSDb I/DZ + P CISD - 189.27209
DZ + P CCSD//DZ + P CCSD - 189.22460
DZ + P CCSDT-lb IIDZ + P CCSD -189.200 59
TZ + 2P CCSD b IIDZ + P CCSD - 189.271 87
• All CISD wave functions employed three frozen core and three deleted virtual orbitals. DZ + P CCSD geom-
etry optimizations included all orbitals. Single point DZ + P CCSD, DZ + P CCSDT-I and TZ + 2P CCSD
wave functions used three frozen core and three deleted virtual orbitals.
b Three frozen core and three deleted virtual orbitals.
by 4.55 to 76.34 kcal mol - I. The extension of the basis set
from DZ + P to TZ + 2P with the CCSD theory gave a
small lowering of 0.47 kcal mol- I in the barrier. These two
effects may be taken as approximately additive 2•3 and thus
the best prediction for the classical barrier height for the
decarboxylation reaction is (80.89-4.55-0.47) = 75.87
kcal mol - I. Such a value is consistent with the predictions of
Ruelle,23 75.97 kcal mol- I, and of Francisco,37 72.8
kcal mol- I.
On a technical note the results in Table III show that the
prediction of the barrier height is not sensitive to the choice
of geometry at which to carry out higher level single point
energy studies. Thus the DZ + P CCSDT-1 prediction for
the decarboxylation barrier at the DZ + P CISD geometry
is 76.54 kcal mol- I while it is 76.34 kcal mol- I at the
DZ + P CCSD geometry. Similarly the TZ + 2P CCSD re-
sult for the activation barrier is 80.45 kcal mol - I at the
DZ + P CISD geometry and 80.42 kcal mol - I at the
DZ + P CCSD structure.
The dehydration transition state structure was found to
be non planar and of C I symmetry (vide infra) and computer
limitations did 'not permit DZ + P CCSD geometry opti-
mization. At the DZ + P CISD geometry DZ + P CCSD
and DZ + P CCSDT-I energies were determined. The clas-
sical barrier height for dehydration (Table IV) is 77.92
kcal mol - I at the DZ + P CCSD level which decreases by
4.21 kcal mol - I with a higher level description of electron
correlation, CCSDT -1. The best prediction for the classical
barrier height to dehydration of formic acid is 73.71
kcal mol - I. Basis set extension effects are likely to lower this
value by -0.5 kcal mol- I if the decarboxylation reaction is
an appropriate guide. Such a classical barrier is in good
agreement with Francisco, 37 74.8 kcal mol-I, at the
MP4/6-311 + + G**/IMP2/6-311G** level. The dehy-
dration and decarboxylation reactions are predicted to have
very similar classical barrier heights with both in the range
74 to 76 kcal mol-I.
The energy predictions for the barrier height to the iso-
merization of trans-formic acid to dihydroxymethylene are
presented in Table V. At the DZ + P CCSD level this classi-
J. Chem. Phys .• Vol. 96. No.2. 15 January 1992
1163
Barrier height
flE (kcal mol- I)
93.84
86.13
82.62
80m
83.85
82.76
79.84
83.77
cal barrier height is 82.76 kcal mol- I which decreases by
2.92 to 79.84 kcal mol-I with the DZ + P CCSDT-I meth-
od. Basis set extension to TZ + 2P with the CCSD approach
leads to a 1.01 kcal mol- I increase in the classical barrier
height relative to the DZ + P CCSD result. Assuming the
additivity of basis set extension and higher order electron
correlation effects the best predicted classical barrier for the
17 August 2023 20:14:11
isomerization offormic acid to dihydroxymethylene is 81.75
kcal mol- I. A value of 83.7 kcal mol- I for this quantity has
been determined by Francisco. 37 Thus the 1,2-hydrogen
shift classical barrier is 6 to 8 kcal mol - I higher than the
comparable quantities for the decarboxylation and dehydra-
tion reactions. Further discussion of the energetics is post-
poned until after the consideration of the predicted harmon-
ic vibrational frequencies which can be used to determine
zero point vibrational energy corrections.
Harmonic vibrational frequencies
The predicted harmonic vibrational frequencies and in-
frared (ir) intensities for trans- and cis-formic acid are re-
ported in Table VI. Theoretical values at both the DZ + P
SCF and DZ + P CISD levels are given as well as the experi-
mental fundamental (anharmonic) vibrational frequencies
of the trans isomer. 35 ,38 The predicted harmonic vibrational
frequencies are not scaled 36 to approximately correct for re-
striction to a particular level of theory or for anharmonic
effects. SCF and CISD methods with DZ + P basis sets typi-
cally give vibrational frequencies which are larger than ex-
periment and anharmonicity corrections of 5% are not unu-
sual. 19
The absolute and relative difference between DZ + P
SCF harmonic frequencies and the observed fundamentals
of trans-formic acid are the same as Ref. 19 to within one
wave number. The present DZ + P CISD predictions of the
harmonic vibrational frequencies of the trans species are in
rather better agreement with experiment. The absolute and
relative difference between DZ + P CISD harmonic fre-
quencies OJ and the observed fundamentals v are 376
cm- ' =1O.5% (VI), 287 cm- ' =9.8% (v2 ), 147
cm- I =8.3% (v3 ), 90 cm- 1 =6.5% (v4 ), 148
1164 Goddard, Yamaguchi, and Schaefer III: Reactions of monomeric formic acid

TABLE VI. Theoretical predictions for the harmonic vibrational frequencies (in cm - J) of trans- and cis-formic acid. Infrared intensities (in km mol - J) are
reported as well. The results from both DZ + P SCF and DZ + P CISD methods are reported.

trans-formic acid ciS-formic acid

DZ+ PSCF DZ+PCISD Experiment" DZ+PSCF DZ+ PCISD

Infrared Infrared Infrared Infrared

Frequency intensity Frequency intensity Frequency Frequency intensity Frequency intensity

Wid 4116 116.3 3945 77.2 3569 4180 121.1 4003 82.4
lU2 a' 3293 52.9 3225 46.3 2938 3208 87.7 3138 81.1
{V3 a' 2015 533.4 1921 422.1 1774 2059 450.9 1962 351.0
It)4 a' 1537 10.5 1470 5.6 1380 1561 5.9 1488 3.1
(Us d 1426 26.1 1366 18.9 1218 1408 434.5 1344 368.8
(£)6 a' 1268 300.8 1203 269.5 1103 1229 26.7 1174 30.5
UJ, a' 690 61.6 649 53.0 626 722 11.6 680 10.8
CtJ8 a" 1183 0.3 1102 0.4 1036 1166 3.1 1084 0.6
(J)9 all 693 200.7 687 175.0 638 503 113.2 507 102.6
ZPVEb 23.2 22.3 22.9 22.0

aR. L. Redington, J. Mol. Spectrosc. 65,171 (1977).

b Zero point vibrational energy in kcal mol- J.

cm- I =12.1% (vs ), 100 cm- I =9.1% (v6 ), 23
cm- I =3.7% (v7 ), 66 cm- I =6.4% (vs ), and 49
cm - I = 7.7% (V9)' The C=O stretch V 3 , C-O stretch V 6 ,
and the torsion V9 are predicted to be the most intense modes
in the infrared spectrum.
Theoretical predictions for the harmonic vibrational
frequencies of the various transition states considered in this
work are collected in Table VII. Both DZ + P SCF and
DZ + P CISD values are reported. The single imaginary vi-
brational frequency for each stationary point confirms that

17 August 2023 20:14:11

Experimental vibrational assignments for cis-formic
acid are not available. The most valuable predictions may be
the shifts in certain bands for the cis-isomer relative to trans-
formic acid. Attention will be focused on the more accurate
DZ + P CISD results. VI' the OR stretch, is blueshifted by
58 cm - I in the cis form as would be expected given that the
OH bond lengths are predicted to be 0.961 A cis and 0.965 A
trans at the DZ + P CISD level of theory. The C=O stretch,
V 3 , increases by 41 cm - I in the cis-formic acid as the bond
length is predicted to decrease by 0.007 A relative to the
trans species. The torsional mode, V 9 , is redshifted by 180
cm - I for the cis species which is less stable than the trans by
-1400 cm - I and thus faces a smaller barrier to rota-
tion. 33 •34
these structures are true transition states. The zero point
vibrational energies, in kcal mol- I, are included and will be
used in the next section to correct the classical barrier
heights.
The imaginary frequency associated with internal rota-
tion is small at 595i cm - I as would be expected given the low
barrier for this process relative to the other three reactions.
For the decarboxylation, dehydration, and isomerization
transition states where the classical barriers are 74 to 82
kcal mol - I the harmonic vibrational frequencies for motion
along the reaction coordinate range from 1919i to 2477i
cm - I (DZ + P CISD). These large imaginary frequencies
suggest significant involvement of hydrogen motion in the
transition states as would be anticipated from consideration

TABLE VII. Theoretical predictions for the harmonic vibrational frequencies (in cm - J) of the internal rotation transition state, the decarboxylation
transition state, the dehydration transition state, and the isomerization to dihydroxy-methylene transition state. The results from DZ + P SCF and DZ + P
CISD methods are reported.

Internal rotation Decarboxylation Dehydration Isomerization

DZ + PSCF DZ+PCISD DZ+PSCF DZ+PCISD DZ+PSCF DZ+PCISD DZ+ PSCF DZ+PCISD

WI a' 4152 4006 2317 2237 4131 3959 3983 3790

lU2 a' 3242 3173 2226 2222 2802 2708 2825 2757
(i)3 a' 2043 1932 1993 1919 2154 2020 1710 1616
Cc)4 a' 1536 1465 1458 1397 1122 1110 1437 1373
a>s a' 1322 1256 1183 (a") 1127 (a") 781 792 1321 1251
lL)6 a' 1244 1170 929 938 514 587 743 (a") 732 (a")
6h a' 1010 954 781 761 462 399 670 635
0)8 a' 740 697 669 (aM) 632 (aM) 276 320 425 (a") 407 (a")
0)9 a' 582i 595i 2684i 2477i 1952i 1919i 2429i 2181i
ZPVEa 21.9 20.9 16.5 16.1 17.5 17.0 18.7 18.0

J
a Zero point vibrational energy in kcal mol

J. Chem. Phys., Vol. 96, No.2, 15 January 1992

 Goddard, Yamaguchi, and Schaefer III: Reactions of monomeric formic acid
of reactants and products or of the saddle point structures in
Figs. 3 through 5. Examination of the eigenvectors associat-
ed with the imaginary vibrational frequencies verify these
inferences. For the dehydration transition state with v* of
1919i cm - I, only H2 (Fig. 4) has large components in the
reaction coordinate. Similarly for the 1,2-hydrogen shift iso-
merization transition state with v* equal to 218li cm - 1, only
the shifting hydrogen makes large contributions to the eigen-
vector. For the decarboxylation transition state, motions of
both hydrogens are involved in the reaction coordinate.
Clearly, substitution of deuterium for hydrogen would yield
interesting isotope effects both due to the changes in zero
point vibrational energies and to quantum mechanical tun-
nelling for these reactions.
Barrier heights and relative energies
Figure 6 illustrates the energies including zero point vi-
brational energy corrections relative to trans-formic acid for
two minima and four transition states on the singlet
HCOOH potential energy hypersurface. DZ + P CISD har-
monic vibrational frequencies were used for the zero point
vibrational energy terms. The energy differences have been
rounded to the nearest kcal mol - 1 and represent our best
current predictions for these quantities. Error bars of ap-
proximately ± 5 kcal mol - 1 could be estimated for the de-
carboxylation, dehydration, and isomerization to :C(OH)2
barrier heights. 2,3 Smaller error bars on the internal rotation
transition state energy and the energy differences between
various stable species would be more appropriate.
The energy difference between trans- and cis-formic
acid of 4 kcal mol - 1 is in excellent agreement with the ex-
perimental value 33 ,34 of 3.900 ± 0.085 kcal mol- I. The pre-
dicted barrier to internal rotation in this work of 12
kcal mol -. 1 is in agreement with several other theoretical
studies. 17,37 One of the more reliable experimental values for
<5
!
w
<l
FIG. 6, Best predictions of the relative energies (in kcal mol- I) of the sta-
tionary points examined on the HCOOH potential energy surface. Zero
point vibrational energy corrections are included in these values.
J. Chem. Phys., Vol. 96, No.2, 15 January 1992
1165
this rotational barrier is 10.9 kcal mol- 1 by Miyazawa and
Pitzer. 40 Francisco37 has predicted an energy difference of
4.1 kcal mol - 1 and an internal rotation barrier of 11.7
kcal mol 1 for the trans-cis formic acid system. Thus where
comparisons of theory and experiment are clearly possible
for the formic acid species, agreement is very good.
The barrier to the 1,2-hydrogen shift from trans-formic
acid to dihydroxymethylene is predicted to be 79
kcal mol - I. Such a value is in general agreement with the
early ab initio results of Feller and Davidson. 2o,21 More sig-
nificantly the predicted value of this study is in agreement
with that ofFrancisc0 37 although somewhat, 5.3 kcal mol- 1
or ~ 7%, higher. Although this barrier to the 1,2-hydrogen
shift is definitely higher than those for the decarboxylation
or dehydration reactions (vide infra), it is not so much
greater as to rule out a priori any dihydroxymethylene in-
volvement in the high temperature thermal chemistry offor-
mic acid. Further study of dihydroxymethylene decomposi-
tions to molecular products (cf. Ref. 20) may be in order.
Prior to considering the decarboxylation and dehydra-
tion reactions a brief consideration of free radical as opposed
to molecular processes will be given. Previous workers lO,I2
have cited reaction energies for radical processes as
+ COOH
HCOOH -+ H· 93 kcal mol- I,
HCOOH-H' + HCOO 106 kcal mol-I,
17 August 2023 20:14:11
and
HCOOH-> 'CHO + 'OH 112.2 kcal mol- I
based on thermochemical data. 39 ,41 These radical heats of
formation should be at least moderately accurate and thus
molecular decompositions of formic acid are clearly pre-
ferred on the ground state surface. Note that the reaction
energies for formic acid decomposing to H 20 + CO and
H2 + CO2 have been determined l2 from thermochemical
data to be 8.31 and - 1.36 kcal mol - I, respectively.
The decarboxylation barrier is 71 kcal mol - I and that
for dehydration 68 kcal mol - I. The fact that the dehydra-
tion reaction has a lower barrier is consistent with those ex-
periments which observed a predominance of CO over CO2
product. 12,14 However, the rather small difference in activa-
tion energies of ~ 3 kcal mol - I may not be large enough to
explain a CO to CO2 ratio of 10 to 1 at the elevated tempera-
tures of the experiments. The predicted barriers are slightly
larger than but in overall good agreement with the threshold
energies of 62 to 65 kcal mol - I for dehydration and 65 to 68
kcal mol- I for decarboxylation determined by Hsu et al. 10
The results for these activation energies in this study are
slightly higher (4.8 or 5.8 kcal mol- I) than those of Fran-
cisco. 37
CONCLUSIONS
The major conclusions of this work may be summarized
briefly as follows:
( 1) The activation barriers for the decomposition of
monomeric formic acid to H2 plus CO2 and to H 20 plus CO
are very similar. The best estimates for the decarboxylation
and dehydration activation energies are ~ 71 and ~ 68
kcal mol- 1, respectively.
1166 Goddard, Yamaguchi, and Schaefer III: Reactions of monomeric formic acid
(2) The barrier height for the 1,2-hydrogen shift from
formic acid to dihydroxymethylene is somewhat higher than
those for the molecular dissociations. The best estimated
barrier is ~ 79 kcal mol - I.
These predicted barriers from higher level theory are in
general agreement with most earlier ab initio studies 22 ,23 and
with very recent research by Francisco. 37 Experimental
reinvestigation of the thermal reactivity of formic acid
would be valuable.
ACKNOWLEDGMENTS
The University of Guelph is thanked for granting the
study leave to J. D. G. which made this collaboration possi-
ble. This research was supported by the U.S. Department of
Energy, Office of Basic Energy Sciences, Division of Chemi-
cal Sciences, Fundamental Interactions Branch, Grant No.
DE-FG09-87ER13811.
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