Dynamics of hydrogen bond exchange in carboxylic acid

dimers8 )
F. Grat, R. Meyer, T. -K. Ha, and R. R. Ernst
Laboratoriumfiir Physikalische Chemie. Eidgeniissiche Technische Hochschule. 8092 Ziirich. Switzerland
(Received 18 May 1981; accepted 11 June 1981)

The simultaneous hydrogen bond exchange within carboxylic acid dimers is investigated by ab initio quantum
chemical calculations and by computations of nuclear dynamics. A significant lowering of the potential
barrier to -60 kJlmol has been achieved by extensive structure optimization. The calculations suggest that
the proton motion is coupled to a deformation motion of the frame of heavy nuclei. The flexible model
treatment of this cooperative nuclear motion yields low vibrational and tunneling frequencies.

I. INTRODUCTION bonds. 10 The data indicated an activation energy in the

The intramolecular two-proton exchange in cyclic
dimers of carboxylic acids has been studied extensively
by experimental and theoretical methods. Electron dif-
fraction data 1• 2 of several such dimers are compatible
with a localized equilibrium structure of type A (or A')
as follows:
Rj Rj
I I
/C~ ~C~
o 0 0"'" "0 0 0
I I
H H
H H
H H
I I
O~ 0 0:-., ,-::0 0",
~C/ '\.C/
I I
R2 R2
A X A'
According to earlier quantum chemical investigations of
the formic acid dimer, 3.4 the interconversion between
nuclear configurations A and A' should involve a simul-
taneous proton exchange across a symmetric transi-
tion structure X lying 160-200 kJ/mol above the
equilibrium structure. On the other hand, experimental
results lead to an estimate of the potential barrier of 80
kJ/mol from infrared measurements 5 on formic acid
dimer itself (R 1 =R 2 = H), and of about 60 kJ/mol from
microwave measurements 6 on mixed aliphatic carboxylic
acid dimers. For formic acid dimer, infrared measure-
ments indicated an upper limit for the double minimum
tunnel splitting of 1012 Hz, 1 and microwave data suggest
a splitting larger than 10 1 Hz for a singly deuterated
mixed bimolecule (R 1 =H, R 2 =CF 3 ).6
Magnetic resonance data in solution have been reported
previously on related systems with intramolecular two-
proton transfer such as porphyrinS and 2, 5-dihydroxy-
p-benzoquinone. 9 They show conclusively a tempera-
ture-dependent proton exchange between symmetrically
equivalent sites. More recently, a solid state NMR in-
vestigation on a series of carboxylic acid dimers (e. g.,
with R j =R 2 = C6H4CH 3 ) has provided direct evidence for
the motion of the hydroxylic protons across the H-
a)Presented in part at the 16th Symposium for Theoretical
Chemistry. Wildhaus. Switzerland. 7-11 September 1980
(Abstract All),
order of 4 kJ/mol and a tunneling rate not larger than
109 Hz. These results cannot be reconciled within the
usual model for the motion of two protons in a symmetric
double well potential of a rigid frame.
Motivated by these observations, the present study has
been undertaken on the model system formic acid dimer
to investigate the importance of cooperative motion of
Rj the heavy nuclei as one possible reason for a reduced
I
barrier and a reduced tunneling rate. Symmetry break-
~C",,- ing of the double well potential by intermolecular inter-
actions can be an additional reason for further slowing
down the exchange. This possibility will, however, not
be discussed here. In analogy to earlier calculations
on other intramolecular proton transfer systems, 11-13
0 careful optimization of skeletal geometry of the
C~ formic acid dimer in an ab initio treatment is found
I to reduce the potential barrier by a considerable amount.
R2
The calculated energy surface suggests, furthermore, a
continuous skeletal distortion occurring along with proton
exchange. The effective mass associated with this cou-
pled nuclear motion varies strongly along the reaction
path and remains substantially larger than the effective
mass for two-proton motion in a rigid frame of heavy
nuclei. As a result, tunnel splittings are reduced by
orders of magnitude.
Related studies published recently include the work by
Kato et al. 14 on the reaction path and vibrational inter-
action effects for proton transfer in malonaldehyde, a
semiclassical treatment of symmetric linear triatomic
double minimum systems by Babamov et al., 15 and a
calculation of Single minimum quantum states by Barton
et al. j6 for FHF-. Little interaction of proton motion
with displacements of the heavy nuclei was found in the
latter case. The situation seems to be different, how-
ever, for formic acid dimer which cannot move from one
of its two equivalent equilibrium configurations to the
other without rearrangement of skeletal nuclei.
II. GEOMETRY OPTIMIZATION OF THE TRANSITION
STRUCTURE
As pointed out by Brickmann and co-workers, an ade-
quate description of the reaction path involves more
structural parameters than just the protoniC coordi-
nates. 3 For this reason, an extensive geometry opti-
mization was carried out for the transition structure X
of the formic acid dimer by means of an SCF ab initio
calculation employing an STO-3G minimal basis set. 17

2914 J. Chern. Phys. 75(6), 15 Sept. 1981 0021·9606/81/182914·05$01.00 © 1981 American Institute of Physics

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 Graf; Meyer, Ha, and Ernst: Dynamics of hydrogen bond exchange 2915

we introduce a variable ~ having values ± 1 at the equilib-

FIG. 1. Numbering of nuclei and
coordinate system for formic acid
dimer.
rium structures A and A', respectively, and the value ~ =0
at the intermediate configuration X. The path of motion
is then specified by the structural parameters S as func-
tions of ~. These functions were defined by quadratic
1
interpolation between equilibrium structures and the
present STO-3G optimized transition structure. In
terms of the coordinates shown in Fig. 1 the path of mo-
tion is given by the following expressions:
carboxylic proton coordinates (in A units)
x(H 1) = -x(H 2 ) = O. 437~ ,
(1)
y(H 1) = -y(H 2 ) =1. 019 +0.142~2 ,

skeletal internuclear distances (in A units)

Assuming D2h symmetry for the configuration X, the
structural parameters, defined in Fig. 1, were opti-
mized as follows: The bond lengths r(C 7 -03) = r(C 1-0 5 )
=r(CS-04)=r(Cs-Os) and the distance r(C 1 '" Cs) as
well as the angles 1:03 CP5 = 1:°4CSOs and 1:CP3 H1
= 1: Cs0 4H2 were varied while the C-H bond was kept
parallel to the C 1-C S direction at a constant length of
1. 09 A. After convergence had been reached, two dif-
ferent out-of-plane deformations of symmetry D2 and C 2h '
respectively, were allowed. The first one corresponds
to a twisting of the -COO groups by an angle ({J (O:s ({J
:s 20 0) between the two -COO planes while the protons
remain in the orginal xy plane. The second one corre-
sponds to a centro-symmetric out-of-plane motion of
the hydroxylic protons alone, characterized by the angle
1>(0:S if> :s 100) between the xy plane and the line connect-
ing the carboxylic protons. None of these deformations
led to further energy decrease with respect to the op-
timized D2h structure. For this transition structure,
the data are given in Table I, along with results obtained
with a 4-21G basis set calculation 18 performed as a test.
III. REACTION PATH AND STATES OF NUCLEAR
MOTION
To describe the motion of the molecular frame asso-
ciated with the double proton exchange within the dimer,
r(C 1-03) =r(C S-04 ) = 1. 287 - O. 055~ + O. 018~2 ,
r(C 1-0 5) = r(Cs-O s) = 1. 287 + O. 055~ + O. 018~2 ,
(2)
r(C 1 '" C 8)=3. 70+0.30e,
r(C 1-H 9 ) =r(C S-H 10) = 1. 09 ,
skeletal angles (in degrees)
1: (03C1CS) = 1: (04CSC1) = 57.0 - 4. O~ + 3. 5~2 ,
1: (05C1CS) = 1: (OsCSC 1) = 57.0 + 4. O~ + 3. 5~2 , (3)
1: (H 9C1CS) = 1: (H 10 C SC 1) = 180. 0 .
The nuclear configurations S(~) and S( -~) are sym-
metrically equivalent. Hence the associated double
minimum potential is also symmetric. 19 The total mo-
lecular energy was subsequently calculated for the values
~=O.O, 0.2,0.4, ... ,1.4, and the resulting points
fitted to a polynomial of the form V(~) = a~2 + b~4 yielding
the potential plotted in Fig. 2. Evidently the potential
minima are quite close to ~ = ± 1, i. e., close to the ex-
perimental equilibrium points. Therefore, we subse-
quently used the form VW = a v( (~2 _1)2 -1]. Wave
functions and energy levels for the coupled nuclear mo-
tion specified by Eqs. (1)-(3) were calculated directly,
using a new flexible model technique. 20 Tunnel splittings
were then obtained as differences between the respec-
tive energy levels.
Of particular interest are the energy of the first vi-
brational transition E 1 -E o and the tunnel splitting in the

TABLE 1. Structural parameters, SCF energies E T , and barrier height av for formic acid dimer
in the equilibrium and transition structures.

D2h Transition structure

Equilibrium structure
(experimental, Ref. 1) S.:rO-3G 4-21G
r(C=O) 1.25 A 1.285 A 1. 28 A
r(C-O) 1. 36 'A 1. 285 'A 1. 28 'A
r(C"'C) 4.0 'A 3.70 'A 3.80 'A
r(O-H"'O) 2.73 A 2.30 'A 2.47 'A
2I,OCO 121. 0" 114.0" 118"
2I,COH 111.6 0
120.0" 120"
gT (a.u.) -372.44829 (STO-3G) -372.42404
- 376.61979 (4-2IG) -376.60045
o.V (kJ!moll 63.6 50.7

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 2916 Graf, Meyer, Ha, and Ernst: Dynamics of hydrogen bond exchange

tion for this.case, i. e., with skeletal coordinates fixed

at their values for ~ = 0 (D 2h skeletal symmetry) are also
shown in Fig. 3.
o. Figure 3(a) demonstrates the Significant lowering of
the vibrational frequency EI-EO by factors 3-5 when full
-20.
structural relaxation is allowed simultaneously with the
double proton motion. Even more dramatic is the de-
-40.
crease of the tunnel splitting toEo by factors of 10 3 _10 5
[Fig. 3(b)1. A comparison with experimental results ob-
-60.
tained from solid state NMR measurements lO suggests
that the proton motion may indeed be Significantly slowed
A x A' down by correlated motion of the molecular frame. Fig-
~------~-------r------~------~ ure 3 shows also that, in the presence of structure re-
-1 o laxation, a much smaller isotope effect can be expected
FIG. 2. Potential energy function V(O. vibrational levels Ev. than for free proton motion.
and ground state tunnel splitting t:.E 0 for coupled proton and The difference between the two types of motion arises
skeletal motion in formic acid dimer. The curve is obtained
from the effect of the kinetic energy coefficient g U which
by fitting the computed energy values (indicated by crosses)
by a fourth order polynomial. is related to the instantaneous mass displacement. 20
The mass is obviously larger for the model including
skeletal relaxation. For this latter case, gH is found to
vibrational ground state AE o, which are plotted for the be strongly varying with ~. It drops by a factor of 15
isotopic modifications (HCOOH}z and (HCOOD)2 in Fig. upon gOing from the transition (~= 0) to the equilibrium
3 as functions of the barrier height AV. For compari- structure (~ = ± 1). This variation of Itt, which is ac-
son we also considered the more traditional case of pro- counted for in the flexible model treatment, 20 implies
ton exchange in a rigid frame as postulated, for example, that the use of a constant reduced mass would probably
in the case of porphyrin. 21 The results from a calcula- not be adequate.

b
a
LOG 4Eo/Hz

12

".
.~
• WITHOUT
..........." skeletal relaxation
1500

-:~
,. .\\.
'0 '", \
WITHOUT
skeletal relaxation
:~
1000 8

6
" '\ \H
~: \.
500

./
.~WITH

01-·-.-'
4
_ _ .---- skeletal relaxation
WITH
H.D skeletal relaxation
4V
..
(kJ/mol) (kJ/mol)
2 4 8 16 32 64 2 4 8 16 32 64

FIG. 3. Vibrational frequency EI-EO and tunnel splitting t:.Eo as functions of the barrier height AV for formic acid dimer with
and without skeletal relaxation coupled to the proton exchange dynamics. Curves are given for proton (H) and deuteron (D) motion
in (HCOOHl 2 and (HCOOD)2. respectively. The curves for El -Eo for the model without skeletal relaxation are not continued below
A V=4 kJ/mol (H) and toV=2 kJ/mol (D) because the tunnel splittings become comparable to the vibrational frequencies and El -Eo
looses its significance.

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 Graf, Meyer, Ha, and Ernst: Dynamics of hydrogen bond exchange 2917

TABLE II. Relative SCF energies E R (C1) =E R(- C -1) (in kJ!moI) calculated with an STO-3G
basis set for independent variations of the collective proton (~) and skeletal distortion (1) coordi-
nates. Values in parenthesis are obtained from the model potential see Eqs. (4) and (5) •

~; 0 0.5 1.0 1.5

1.5 670 (1194) 662 (1170) 296 (397) 7.3 (7.9)

1.0 228 (229) 69.8 (67.3) -65.3 (-67.9) 461 (532)
0.5 10.6 (B.5) -34.2 (-27.7) 376 (352) 2269 (1911)
0 0.0 (0.0) 78.9 (76.8) 89B (B03) 3315 (3417)
-0.5 10.6 (8.5) 81. 3 (79.6) 710 (711) 24BB (35B3)
-1.0 22B (229) IBO (177) 305 (31B) 10BB (2239)
-1. 5 670 (1194) 6B3 (714) 444 (257) 469 (716)

IV. POTENTIAL ENERGY COUPLING OF SKELETAL
AND PROTON MOTION
In the previous section we assumed a strong coupling
of Skeletal and proton motion, which would correspond
to the existence of a deep and narrow channel in the po-
tential energy surface connecting the two configurations.
To test this assumption we parametrized the skeletal
distortion independently by a second variable 1). We
therefore replaced ~ by 1) in Eqs. (2) and (3) [leaving
Eq. (1) unchanged] and calculated ab initio energies as a
function of both ~ and 1). The pOints (~,1)==(1, 1) and
(~,1) == (- 1, -1) correspond to the equilibrium configura-
tions A' and A, respectively, while the pOint (0,0) gives
the D2h intermediate X [Fig. 4(b) J. A new configurationB
at (1, - 1) is reached from A by transferring the carboxylic
protons while keeping the positions of the other nuclei fixed.
The symmetrically equivalent configuration B' at (~,1)
==(-1,1) can similarly be reached from A'. The poten-
tial energy values calculated with an STO-3G basis set
are collected in Table II. In order to obtain an accept-
able analytical representation of the potential surface
V(~, 1) we applied various interpolation schemes with
little success. Therefore, an attempt was made to con-
struct a model surface as a function of better adapted
coordinates
The leading term was formed by the symmetric double
minimum profile through configurations A, X, and A',
as given above, and the dependence on 1)' was.approxi-
mated by third order polynomials in 1)', with coefficients
depending on ~'. The model function obtained for V in
kJ/mol
V(e, 1)') == -125 (e)2 + 57(e)4 + [318 + 7877(e)2
-1760(e)4](1)')2 -{[385~' + 838(~')3]!
[1 + 2, 3(n S
]}. [1)' + 4(1)')3]
approximates the low ab initio energies with fair accu-
racy (see Table II) while larger deviations are allowed
for at high energies. In the present study aiming at an
investigation of the proton dynamics, numerical accu-
racy is less important in regions of high energy. In
such regions the computed ab initio values themselves
are not very reliable due to intrinsic limitations of the
quantum chemical method used, but are nevertheless
helpful in determining the qualitative form of the poten-
tial.
A contour diagram of the model function is shown in
Fig. 4. Evidently this function does contain a low en-
ergy channel connecting the two equilibrium configura-
tions A and A'. Near the intermediate configuration X,
which corresponds to a saddle point, the channel widens
considerably, expanding towards configurations B and B'.
V. DISCUSSION
In comparison with earlier studies3•4 the barrier ~ V
separating the configurations A and A' of formic acid
dimer is lowered from 200 kJ/mol to 60 kJ/mol as a
result of geometry optimization including the distance
between monomer constituents. The distance between
hydrogen-bonded oxygens drops from 2.73 'A at equilib-
rium to 2.30 'A in the D2h symmetric intermediate X.
Similar contractions were found for one-proton transfer
systems. 11-13
The coupled motion of protons and molecular frame
through the points A-X-A' [Eqs. (1) to (3)] yields a
ground state tunnel splitting ~Eo smaller by 3-5 orders
of magnitude than the splitting obtained with fixed heavy
atoms.
The potential surface obtained as a function of indepen-
dent proton transfer and skeletal relaxation coordinates
contains a low energy channel connecting the configura-
(4)
tions A -x -A', thus supporting the concept for a one-
dimensional motion that corresponds approximately to a
straight line through these points (cf. Fig. 4). The pro-
nounced widening of the channel near the saddle point X
has a number of consequences for a more detailed de-
scription of the proton exchange process:
(i) The molecular structure at the saddle point be-
comes soft in the sense that deviations from the one-
dimensional reaction path require little energy.
(5) (ii) Within the one-dimensional treatment, the effec-
tive barrier is further lowered by a reduction of the vi-
brational zero point energy near the saddle point. 14
(iii) Reaction paths bypaSSing the intermediate con-
figuration X must be included in a statistical average of
the motional process, thus enhancing the entropy of ac-
tivation for the proton exchange.
The potential surface of Fig. 4 may also be used for
a schematic representation of alternative reaction path-
ways which have been proposed earlier for formic acid
dimer. For instance, a mechanism of typeA:B:A'

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 2918 Graf. Meyer. Ha. and Ernst: Dynamics of hydrogen bond exchange

'1 "
1
.z:r- ,t 8 1
--(::r~

-1
I -<-----r
--e--
.. ~

-1
-<.:)- -,t -\::)-A 8
-1 0 1 ~

a b
FIG. 4. (a) Potential surface of formic acid dirner, according to Eqs. (4) and (5) for independent proton (0 and skeletal motion (11).
(b) Nuclear configurations are shown for the saddle point (X), for the equilibrium structures (A,A '), and for the structures (E, B')
obtained by proton transfer with fixed frame. The nuclear positions of the transition structure X are indicated for reference by
open circles in the drawings for A,A • and B, B ••

:: B'::A involving a proton transfer within a rigid frame
as the first step has been investigated by Clementi. 22
On the contrary, in a recent paper by Sokalski 23 the in-
terconversion reaction is thought to be initialized by a
purely skeletal distortion of A followed by proton tunnel-
ing. In view of the high energy regions crossed by these
two alternative paths, they appear less favorable than
the direct interconversion A::X ::A' with simultaneous
structure relaxation.
When comparing the presented theoretical results,
which suggest a concerted motion of proton pair and mo-
lecular skeleton, with measurements in liquid or solid
phase, the possibility of strong perturbations by inter-
molecular interactions has to be taken into account. The
local environment may significantly alter the potential.
An example of such a situation will be discussed at an-
other occasion. 10
In a very recent paper on tunneling in formic acid
dimer, which appeared after completion of this work,
Agresti et al. 24 computed a barrier 30-40 kJ/mOI higher
than the present value. Their calculations on tunneling
rates involve a constant reduced mass which corre-
sponds to linear double proton motion in a rigid frame of
heavy nuclei, whereas we emphasize in our treatment
the effects of coupling of the proton dynamics with the
motion of the heavy nuclei.
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