THE JOURNAL OF CHEMICAL PHYSICS 124, 074511 共2006兲

The water exchange process of tetraaquaplatinum„II…:

Density-functional theory and ab initio computational study
Partha Sarathi Senguptaa兲
A.M. College, Jhalda, West Bengal 723202, India
共Received 4 November 2005; accepted 21 December 2005; published online 21 February 2006兲

The water exchange process of square planar tetraaquaplatinum共II兲 was computationally

investigated at the Hartree-Fock, density-functional theory 共B3LYP, PW91PW91, and mPW1PW91兲
and the second-order Møller-Plesset perturbation theory of levels of calculation. The stationary
points on the gas phase and on the reaction field potential-energy surface were fully optimized and
characterized. The self-consistent reaction field 共SCRF兲 methods were also applied on the same
system. The structures and energetic processes of all the species involved were investigated. The
kinetic and thermodynamic properties for the gas phase and SCRF model data were compared with
the available experimental data. The rate constants in MP2 level of theory and B3LYP isodensity
polarized continuum model reaction field are in good agreement with the experimental data.
© 2006 American Institute of Physics. 关DOI: 10.1063/1.2167643兴

I. INTRODUCTION constants were calculated as a function of level of theory and

Substitution reactions of square planar platinum共II兲 com-
plexes were extensively studied and invariably attended by a
large negative entropy of activation 共⌬S‡兲 and a negative
volume of activation 共⌬V‡兲. This is consistent with the asso-
ciative mode of activation. On the other hand, very few sol-
vent exchange kinetics of square planar platinum共II兲 com-
plexes were investigated.1–3 However, exchange reactions
between the solvated cation and the bulk solvent are more
fundamental compared to ordinary substitution reaction as
the entropy of activation 共⌬S‡兲 is more easily interpreted for
reactions which do not involve any net chemical change.4
Water exchange reactions of tetraaquaplatinum共II兲 was
investigated experimentally by following the increase in
height of O17 NMR signal from coordinated water obtained
when platinum共II兲 perchlorate solution was mixed with O17
enriched water.1 The O17 NMR data reveals negative entropy
of activation 共⌬S‡兲 and negative volume of activation 共⌬V‡兲
in support of associative mechanism. The same reaction was
studied by measuring the Pt195 NMR linewidth of the reso-
nance from coordinated water. The approximate activation
entropy found was slightly positive and as such the intimate
mechanism changes from associative interchange 共Ia兲 to dis-
sociative interchange 共Id兲.2
In the present work, the author attempts to analyze this
water exchange reaction
关Pt共H2O兲4兴2+ + H2O17 7a关Pt共H2O兲3共H2O17兲兴2+ + H2O 共1兲
using quantum chemical ab initio methods as ab initio and
density-functional theories are now used extensively for the
study of structural, electronic, and dynamical properties of
different systems in chemistry and other related fields.5–8
Helm et al. have reported the experimental data for this
reaction.1 The structure, thermodynamic properties, and rate
a兲
Electronic mail: anapspsmo@yahoo.co.in
compared with the results reported earlier. Additionally the
solvent effect on the thermodynamic and kinetic properties
for this reaction was analyzed employing different self-
consistent reaction field 共SCRF兲 models. It is believed that
the theoretical analysis reported here can provide valuable
chemical information about important aspects of water ex-
change reaction of tetraaquaplatinum共II兲 ion.
II. METHODOLOGY
Full unconstrained geometry optimization and frequency
calculation for all the distinct species involved in the water
exchange process of tetraaquaplatinum共II兲 have been carried
out at the Hartree-Fock 共HF兲 and second-order Møller-
Plesset perturbation theory. Three density-functional meth-
ods have also been done on the same process. These are 共a兲
the original Perdew-Wang exchange functional and Perdew-
Wang 91 gradient corrected correlation functional
共PW91PW91兲,9,10 共b兲 three parameter fit nonlocal correlation
provided by LYP expression and VWN functional III for
local correction and exchange functional suggested by
Becke11–14 共B3LYP兲, and 共c兲 modified Perdew-Wang ex-
change and Perdew-Wang 91 correlation 共MPW1PW91兲.15
The standard split valence basis set 6-31G共d兲 共Refs. 16 and
17兲 was applied for O and H atoms. The relativistic effective-
core potential 共ECP兲 and associated valence double ␰ basis
set of Hay and Wadt18,19 共LANL2DZ兲 was employed for Pt.
This includes electrons in the 6s, 6p, and 5d orbitals. All
stationary points located on the potential-energy surface
were characterized as minima 共no imaginary frequencies兲 or
first-order transition state 共characterized by having one
imaginary frequency兲 through harmonic frequency calcula-
tions. To gain deeper insight into the reaction pathway,
the intrinsic reaction coordinate 共IRC兲 was calculated
using Gonzalez-Schlegel second-order path following al-
gorithm20,21 starting from the optimized transition state struc-
ture with a step size of 0.100 共amu兲1/2 bohr. The minimum

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074511-2 Partha Sarathi Sengupta J. Chem. Phys. 124, 074511 共2006兲

FIG. 1. B3LYP optimized structures for the species involved in the water FIG. 2. Representation of the imaginary normal mode calculated at the
exchange process of tetraaquaplatinum共II兲. B3LYP level of theory for the transition state.

energy path used in IRC is defined as the path that would be
taken by a classical particle sliding downhill with infinitesi-
mal velocity from the transition state to each minima. Ther-
mal contributions to the energetic properties were also cal-
culated at 298.15 K and 1 atm.
To incorporate the solvent effects in this exchange reac-
tion, two self-consistent reaction field models have been uti-
lized. These are the Onsager22–27 reaction field model and
the isodensity polarized continuum model 共IPCM兲.28 In the
Onsager reaction field model, the solvent is considered as a
continuous unstructured dielectric with a given dielectric
constant surrounding a solute embedded in a spherical cavity.
In IPCM, the cavity is defined by the isosurface of the total
electron density calculated at the level of theory being ap-
plied. The integration of this surface can be carried out by
gradient vector field or by using the center of nuclear charge.
The electronic environment will thus derive the cavity
uniquely.
The rate constant 共k兲 has been evaluated according to
Eyring’s transition state theory,
k共T兲 = 共kBT兲/h exp共− ⌬G‡/RT兲,
where kB is the Boltzmann constant, T the absolute tempera-
ture, and h the Planck constant. ⌬G‡ is the free energy of
activation for each step. All the quantum-mechanical calcu-
lations have been carried out with the GAUSSIAN 03
program.29
III. RESULTS AND DISCUSSION
A. Structural analysis
Figure 1 shows all optimized structures found on the
potential-energy surface for the species involved in the water
exchange process of tetraaquaplatinum共II兲. For clarity, only
the B3LYP structures are shown. A systematic search for the

TABLE I. Structural analysis for the transition state 共TS兲 in gas phase of the water exchange reaction. In
parentheses are the respective values in Onsager reaction field model.

Bond lengths
共Å兲 HF MP2 B3LYP PW91PW91 mPW1PW91

Bond lengths 共Å兲

Pt– Oeq 2.43共2.45兲 2.396a 2.424共2.443兲 2.430共2.443兲 2.395共2.408兲
17
Pt– Oeq 2.42共2.43兲 2.384 2.407共2.422兲 2.413共2.422兲 2.379共2.387兲
Pt–O 共T兲b 2.14共2.104兲 2.104 2.123共2.107兲 2.122共2.112兲 2.096共2.087兲
Pt– Oax 2.07共2.071兲 2.059 2.068共2.072兲 2.072共2.073兲 2.047共2.048兲
Pt– Oax 2.049共2.052兲 2.049 2.055共2.059兲 2.059共2.062兲 2.035共2.037兲
O–H 0.958共0.959兲 0.983

Bond angles 共degrees兲

O共T兲 – Pt– O17 143.5共143.3兲 147.3 148.1共147.2兲 149.4共148.8兲 147.9共147.4兲
O共T兲 – Pt– Oeq 146.3共147.0兲 145.9 145.8共146.8兲 145.6共146.9兲 145.8共146.5兲
O17 – Pt– Oeq 69.2共68.3兲 66.6 65.9共65.8兲 64.8共64.9兲 66.1共66.0兲
O17 – Pt– Oax 96.4共98.4兲 101.8 104.2共104.2兲 106.1共106.2兲 104.0共104.0兲
O17 – Pt– Oax 81.6共79.6兲 74.9 72.4共72.8兲 70.4共70.6兲 72.87共73.1兲
Oeq – Pt– Oax 88.3共87.4兲 86.98 86.4共85.8兲 85.4共84.8兲 86.6共86.2兲
Oeq – Pt– Oax 89.6共89.1兲 86.7 87.6共88.8兲 84.8共84.4兲 87.6共88.4兲
Oeq – Pt– Oax 177.0共176.9兲 173.6 173.9共174.6兲 173.5共173.9兲 174.2共174.6兲
a
Only single-point PSCF with Onsager reaction field.
b
O 共T兲 is the trans O to the leaving OH2 in the original complex, 关Pt共H2O兲4兴2+.
074511-3 Water exchange of tetraaquaplatinum共II兲
FIG. 3. Variation of Pt–O and Pt– O17 bond length in different levels of
theory for the exchange process.
intermediate structures was done and five stationary points
along the reaction pathway were found as can be seen in Fig.
1. The reactant molecule shows almost a square planar ge-
ometry around the central Pt atom. The Pt–O and O–H bond
lengths are 2.067 and 0.98 Å at B3LYP level of theory. The
bond angles are 90.01°, 89.95°, 89.99°, and 90.0°,
respectively.
FIG. 4. 共a兲 IRC analysis for the water exchange process of tetraaquaplati-
num共II兲; 共b兲 change in Pt–O and Pt– O* bond length along the IRC.
J. Chem. Phys. 124, 074511 共2006兲
FIG. 5. HOMO-LUMO energy gap 共ev兲 for all species involved in the water
exchange process of tetraaquaplatinum共II兲.
In the intermediate I1, 关Pt共H2O兲4兴2+ ¯ H2O17, the in-
coming isotopic water is strongly hydrogen bonded with the
two hydrogen of two aqua ligands at an intermolecular dis-
tance of 1.728 and 1.721 Å, respectively. The existence of
hydrogen bond was supported by the depression of stretching
frequencies30 by 460 cm−1.
In this substitution reaction, a five coordinated trigonal-
bipyramid-like transition state with a small leaving H2O – Pt
and entering H2O17 angle, i.e., 65.95°, was found. The tran-
sition state 共TS兲 structure has an imaginary frequency of
−182 cm−1 computed at B3LYP level of theory in which the
Pt–O 共2.424 Å兲 bond is breaking and the Pt– O17 共2.407 Å兲
bond is forming, the Pt–O共T兲 bond length in the equatorial
plane has larger value than the two axial Pt–O bond lengths.
Figure 2 represents the imaginary normal mode calculated at
B3LYP level of theory. The imaginary frequency at MP2
level is −192 cm−1. In the intermediate structure I2, the leav-
ing aqua ligand, H2O is hydrogen bonded with intermolecu-
lar distance of 1.733 and 1.712 Å, respectively and partially
coordinated with the hydrogen of the incoming isotopic wa-
ter. The final product P has an almost square planar geom-
etry around the Pt atom; H2O17 completely replaced H2O.
From the structural data 共Table I兲, it can be seen that there
occurs a great variation in bond lengths in the equatorial
plane of the distorted trigonal-bipyramid-like transition state
during the exchange process which resembles the mechanis-
tic interpretation of substitution reaction of square planar
Pt共II兲.31
The change in bond lengths on the reaction center for the
reactant, transition state, intermediates, and products are
plotted in Fig. 3. The values for different levels of theory are
shown for comparison.
The geometries I and II 关Fig. 4共a兲兴 in intrinsic reaction
coordinate were fully optimized at the B3LYP level of theory
and were found to be the correct intermediate structures 共I1
and I2兲. The respective changes in bond lengths 共Pt–O and
Pt– O17兲 are also plotted in Fig. 4共b兲.
This exchange reaction was characterized by replace-
ment of H2O by H2O17 and proceeds via a collision between
074511-4 Partha Sarathi Sengupta J. Chem. Phys. 124, 074511 共2006兲

TABLE II. Total energy 共E兲 and Gibbs free energy 共G兲, in hartees for the reaction intermediates 共I1 and I2兲 and
the transition state of the water exchange reaction. Gibbs free energy is obtained after thermal correction to
Gibbs free energy with respective scale factor of level of theory 共Ref. 32兲.

HF MP2 B3LYP PW91PW91 mPW1PW91

I1
Gas E −497.818 168 −497.808 968 −500.672 621 −500.600 827 −500.590 057
G −497.738 787 −497.719 591 −500.581 877 −500.512 401 −500.497 490
Onsager E −497.819 937 −498.850 965 −500.673 314 −500.600 075 −500.590 561
a
G −497.730 324 −500.583 218 −500.512 266 −500.498 454
b
IPCM E −487.635 089 −490.469 946 −490.385 096 −490.381 095

TS
Gas E −497.783 202 −497.773 384 −500.628 385 −500.556 300 −500.545 162
G −497.696 809 −497.685 851 −500.539 839 −500.469 589 −500.454 467
Onsager E −497.785 929 −498.812 546 −500.631 249 −500.558 329 −500.547 132
a
G −497.698 576 −500.543 139 −500.472 182 −500.456 727
b
IPCM −487.612 986 −490.437 207 −490.354 838 −490.354 104

I2
Gas E −497.812 534 −497.809 494 −500.673 208 −500.601 392 −500.590 701
G −497.726 375 −497.719 588 −500.582 112 −500.513 312 −500.497 657
Onsager E −497.814 364 −498.851 183 −500.673 365 −500.601 689 −500.590 868
a
G −497.726 374 −500.583 008 −500.514 227 −500.498 360
b
IPCM −487.641 421 −490.470 031 −490.385 133 −490.381 175
a
Only single-point PSCF is possible.
b
Convergence not achieved in GAUSSIAN 03W framework.

the reactant 关Pt共H2O兲4兴2+ with the nucleophile species
H2O17. In such substitution process, a five coordinated dis-
torted trigonal-bipyramid-like transition structure, with enter-
ing ligand, leaving ligand, and the metal complex being
weakly bound was found. This was found to be true from the
structural analysis 共Table I兲. The small angle between enter-
ing H2O and leaving H2O17 minimizes the repulsion between
the d orbital electrons of Pt and the electron pairs of the
entering and the leaving groups. From structural analysis, it
was concluded that the main geometric change took place in
the equatorial plane of the transition structure 共in both gas
and SCRF model兲. In the d8 trigonal-bipyramid transition
state, there occurs greater interaction among the filled d␲
orbital electrons with the equatorial ligands compared to the
axial ligand. Henceforth d␲-p␲* back bonding and d␲-p␲
nonbonding repulsions affect the trigonal plane mainly.
Population analysis of the transition state from the opti-
mized structure in B3LYP levels of theory reveals that the
main contribution of highest occupied molecular orbital
共HOMO兲 and lowest unoccupied molecular orbital 共LUMO兲
comes from d atomic orbital of the Pt atom. It was also
observed that throughout the reaction path, the energy of
HOMO remains constant but the energy of LUMO increases
steadily leading to a decrease in gap between HOMO and
LUMO as shown in Fig. 5.

TABLE III. Rate constant 共k兲 and free energy of activation 共⌬G‡ in kJ mol−1兲 for forward and reverse exchange
processes are shown in different levels of theory and SCRF model. Rate constants in s−1.

HF MP2 B3LYP PW91PW91 mPW1PW91 Expt.

Forward reaction
Gas ⌬G‡1 83.9582 88.5843 110.3707 112.4028 112.9568 92.37a
k1 1.21⫻ 10−2 1.87⫻ 10−3 2.85⫻ 10−7 1.25⫻ 10−7 1.01⫻ 10−7 3.9⫻ 10−4a
Onsager ⌬G‡1 83.3517 100.8691 105.2274 105.2405 109.5542
k1 1.54⫻ 10−2 1.32⫻ 10−5 2.27⫻ 10−6 2.26⫻ 10−6 3.97⫻ 10−7
IPCM ⌬G1 ‡
58.031 42 ¯ 85.9562 79.4423 70.8648
k1 4.23⫻ 102 ¯ 5.42⫻ 10−3 7.5⫻ 10−2 2.381
Reverse reaction
Gas ⌬G−1‡
77.6255 88.5764 110.9877 114.7947 113.3953
k−1 1.56⫻ 10−1 1.88⫻ 10−3 2.22⫻ 10−7 4.79⫻ 10−8 0.84⫻ 10−7
Onsager ⌬G−1 ‡
72.9836 101.4414 104.1693 110.3891 109.3074
k−1 1.014 1.05⫻ 10−5 2.84⫻ 10−6 2.83⫻ 10−7 4.38⫻ 10−7
IPCM ⌬G−1‡
74.656 08 ¯ 86.1794 79.5395 71.0749
k−1 0.517 ¯ 4.95⫻ 10−3 7.21⫻ 10−2 2.19
a
Reference 1.
074511-5 Water exchange of tetraaquaplatinum共II兲 J. Chem. Phys. 124, 074511 共2006兲

TABLE IV. Thermodynamic parameters for the exchange process 共⌬G‡ and ⌬H‡ are in kJ mol−1 and ⌬S‡ in
J K−1 mol−1兲.

HF MP2 B3LYP PW91PW91 mPW1PW91 Expt.

⌬G‡1 83.9582 88.5843 110.3707 112.4028 112.9568 92.37

⌬G−1
‡
77.6255 88.5764 110.9877 114.7947 113.3953 ¯
⌬H‡1 86.00 90.61 111.16 116.46 114.71 89.7± 2.4
⌬H−1
‡
84.12 90.74 112.59 117.56 115.15
⌬S1
‡
−6.3 −6.8 −1.5 −9.6 −5.8 −9 ± 8
⌬S−1
‡
−21.2 −7.2 −4.2 −9.3 −5.5

B. Solvent effect on the structural properties
This section compares the structural data in Onsager
self-consistent reaction field model, i.e., solution phase with
the gas phase data for the transition state. All the bond
lengths increase in Onsager model except the equatorial
Pt–O共T兲 bond of the distorted trigonal-bipyramid-like transi-
tion state 共Table I兲. The changes in bond angle are less sig-
nificant except the equatorial angles. The angle between the
entering H2O and leaving H2O17 is almost constant but the
other two equatorial angles change their values in all the
levels of theory concerned. This also favors the conclusion
that main geometric change took place in the equatorial
plane during the exchange process.
activation 共⌬S‡兲. The ⌬H‡ values are close to 110 kJ mol−1
for the forward process and 114 kJ mol−1 for the reverse pro-
cess for all the DFT levels of theory done.
The rate constants were calculated according to the tran-
sition state theory 共Table III兲. Analysis of the data revealed
that the values of rate constant for the forward process in
MP2 level of theory 共k1 = 1.87⫻ 10−3 s−1兲 and in B3LYP with
IPCM reaction field 共5.42⫻ 10−3 s−1兲 were in close agree-
ment with the experimental data. The solvent effect on ⌬G‡
and ⌬H‡ was not large compared to that of the IPCM reac-
tion field. Yet it affects the rate constants considerably. The
differences in ⌬G‡ were within range, the rate constants vary
from 4.23⫻ 102 to 1.01⫻ 10−7 s−1. However, the IPCM rate
constants were greater than the experimental rate constants.

C. Kinetic analysis
The total energy 共E兲 and Gibbs free energy 共G兲 of the
intermediate species and the transition state for the exchange
process are given in Table II. It was found from Table II that
the data of the Hartree-Fock 共HF兲 level of theory are incon-
sistent compared to the other levels of theory. The free en-
ergy of activation was almost constant for all the density-
functional methods 共within 2.5 kJ mol−1兲. The corresponding
value for MP2 level of theory was close to the experimental
value but the computational cost was very high. The free
energy of activation 共⌬G‡兲 and enthalpy of activation 共⌬H‡兲
were lower at the HF and MP2 levels compared to those of
the three density-functional theory 共DFT兲 methods 共Tables
III and IV兲.
In both the forward and reverse exchange processes, en-
thalpy of activation 共⌬H‡兲 and entropy of activation 共⌬G‡兲
were very similar with a small contribution of entropy of
FIG. 6. Energy profile for the water exchange process
tetraaquaplatinum共II兲.
IV. CONCLUSION
In the present study, the author analyzed the mechanism
of water exchange reaction of 关Pt共H2O兲4兴2+ using ab initio
and density-functional methods. Structural parameters, en-
ergy differences 共Fig. 6兲 共⌬G‡ and ⌬H‡兲, and rate constants
were calculated and compared with the available experimen-
tal data. The existence of a pentacoordinated transition state
with negative entropy of activation 共⌬S‡兲 and high enthalpy
of activation 共⌬H‡兲 suggest an associative mechanism. The
reaction pathway was confirmed by the IRC analysis.
The rate constants calculated at B3LYP protocol in
IPCM 共0.542⫻ 10−4 s−1兲 and MP2 gas phase 共0.187
⫻ 10−4 s−1兲 were in agreement with the experimental value
共3.9⫻ 10−4 s−1兲.
ACKNOWLEDGMENTS
The author thanks the UGC, New Delhi for granting a
minor Research Project 关No. FPSWNO 009/03-04 ERO Sl.
No. 47303兴. The author also thanks Dr. Parimal Kumar Das,
Krishnendu Kundu, and Sukanta Mondal for their sugges-
tions. The author thanks CHEMCRAFT for their free internet
version.
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