Comparison between Optimized Geometries and Vibrational Frequencies Calculated by the

DFT Methods
A. A. El-Azhary*
,
Institut fur Theoretische Chemie, UniVersitat Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
H. U. Suter
Institut fur Physikalische und Theoretische Chemie, UniVersitat Bonn, Wegelerstrasse 12,
D-53115 Bonn, Germany
ReceiVed: February 29, 1996; In Final Form: June 11, 1996
X
Optimized geometries, vibrational frequencies, and scale factors were calculated for furan and thiophene
with the HF, MP2, LDA, BVWN, BLYP, and B3LYP methods of theory using the 6-31G**, cc-pVDZ, and
cc-pVTZ basis sets. The agreement between the optimized and experimental geometries was in the order
B3LYP, MP2, LDA, BVWN, BLYP, then HF. The calculated frequencies by the unscaled BVWN force
field had the smallest average error in the mid-IR region, but using one-scale-factor scaling, those calculated
by the scaled B3LYP force field had the lowest average error. Using one-scale-factor scaling, scale factors
of 0.82, 0.89, 0.98, 0.93, 0.96, and 0.96 were obtained by the HF, MP2, BLYP, B3LYP, LDA, and BVWN
force fields, respectively, using the 6-31G** basis set. The effect of the basis set on the calculated bond
angles, frequencies, and scale factors by the DFT methods was minor, but except with the LDA method, the
agreement between the calculated and experimental bond lengths can be arranged in the order cc-pVDZ,
6-31G**, then cc-pVTZ basis set.
Introduction
The study of vibrational spectra of small organic molecules
is greatly enhanced by the help of ab initio calculations, which
are in principle able to reproduce the harmonic force fields to
any desired accuracy. Despite this theoretical possibility, it is
often useful to work with scaled force fields, in the way defined
by the pioneering work by Pulay and co-workers.
1
This scaling
procedure will take into account the inadequacy of the methods
(missing correlation, basis set effects) as well as the anharmo-
nicity of the potential. To be a reasonable starting point for a
scaling procedure, the used method must show a systematic
behavior. For the Hartree-Fock procedure, for example, it is
known that the frequencies are uniformly overestimated by about
10%. The advance in computer hardware and the desire to get
more accurate predictions of the vibrational spectra mobilized
the use of the more time consuming methods, including electron
correlation. The simplest of these methods is the Mller-
Plesset (MP2) method,
2
which gained interest especially after
the development of the force fields and diople moment
derivatives calculated by the analytical method.
3
Typically, the
MP2 frequencies are overestimated by about 5%.
4
Although
the MP2 force fields gained some interest for the vibrational
analysis,
5-12
MP2s computational demand still limited its wide
application.
Recently, the DFT method was introduced for the vibrational
analysis. The DFT method gained interest due to its excellent
accuracy to CPU time ratio.
13
Currently, three types of density
functionals are in commen use. The first type uses only a
function of the electron density and is sometimes called local
density approximation (LDA). The VWN (Vosko-Wilk-
Nussair) functional
14
belongs to that class. The second type
also uses the gradient of the electron density in the functional;
from those the Becke correction
15
seems to be the most
prominent. Therefore, the BVWN and BLYP functionals belong
to that class. The development of mixed functionals
16
defines
a third class. In these functionals the different terms are mixed
with empirically determined parameters. The so-called B3LYP
functional
13
will be used as an example of that class of
functionals. It is hoped that the quality of the calculation is
improved in the chain LDA < (BVWN, BLYP) < B3LYP.
There are already several publications that compare these
functionals.
1-13,17-20
In addition, in a previous publication we
compared the optimized geometries, frequencies, intensities,
scale factors, and scaled force fields calculated by the HF, MP2,
and B3LYP methods.
21
But in these publications, the most
promising B3LYP functional was not considered (since these
publications were reported before the development of the
B3LYP functional), the basis set effect was not considered
(although this is expected to have minor effect,
18,19
) or the
calculated vibrational intensities
13
or the scale factors
20
were
the main interest.
The aim of the present publication is to investigate in detail
the differences between the optimized geometries, frequencies,
and scale factors calculated by the BLYP, B3LYP, LDA, and
BVWN methods in addition to the HF and MP2 methods.
Further, to investigate the basis set effect, three basis sets were
chosen. These are the 6-31G**, cc-pVDZ, and cc-pVTZ basis
sets. The two molecules furan and thiophene were selected for
this investigation, because on one hand they are rather well
characterized experimentally, while on the other hand they are
large enough not to be trivial cases. Both molecules have been
the subject of detailed vibrational analysis
22,23
and normal
coordinate analysis using empirical force fields.
24
Harmonic
frequencies and IR absorption intensities at the MP2/DZP level
were also reported for both molecules.
5
* Author to whom correspondence should be addressed.

Permanent address: Department of Chemistry, Faculty of Science, Cairo

University, Giza, Egypt. E-mail: Azhari@frcu.eun.eg.
X
Abstract published in AdVance ACS Abstracts, August 15, 1996.
15056 J. Phys. Chem. 1996, 100, 15056-15063
S0022-3654(96)00618-1 CCC: $12.00 1996 American Chemical Society
+ +
+ +
Computational Details
The calculations were done with the HF,
25
MP2,
2
BLYP,
26
B3LYP,
13
LDA,
14
and BVWN methods using the 6-31G**,
27
cc-pVDZ,
28
and cc-pVTZ
28
basis sets. The MP2 calculations
were performed with and without correlating the 1s orbitals of
the heavy elements acronymed as fixed core (fc) and MP2-
(full). The MP2 calculation with the cc-pVTZ basis set was
not performed due to the large amount of CPU time required.
The number of basis functions used for furan/thiophene with
the 6-31G**, cc-pVDZ, and cc-pVTZ basis sets are 95/99, 90/
94, and 206/210, respectively. The geometry optimization and
force field calculations were done under the C
2V
symmetry
constraints. All calculations were done using the Gaussian94
29
program except those at the HF/6-31G** and MP2/6-31G**
levels for both molecules and the MP2/cc-pVDZ level for furan,
where the CADPAC
30
program was used. For calculations with
the Gaussian program and at the HF/6-31G** level with the
CADPAC program, the force fields were obtained analytically
at the corresponding optimized geometries. For those calculated
with MP2/6-31G** for furan and thiophene and MP2/cc-pVDZ
for furan, the force fields were calculated numerically, at the
corresponding optimized geometry, using the simplex algorithm
with a step size of 0.001 bohr. To minimize the translational
and rotational contamination of the force fields calculated
numerically, the optimized geometries were obtained with the
largest component of the Cartesian energy gradient of less than
10
-5
hartree/bohr. While for those calculated at the HF/6-
31G** level the largest component of the Cartesian energy
gradient was less than 10
-4
hartree/bohr. For those calculated
with the Gaussian program, the default parameters were used.
Results and Discussion
Optimized Geometries. The theoretically optimized and
experimental geometries determined for furan and thiophene
TABLE 1: Equilibrium Geometry for Furan
6-31G**
coor-
dinate exptl
b
HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
O1-C2 1.362 1.343 1.364 1.366 1.382 1.364 1.351 1.383
C2dC3 1.361 1.339 1.365 1.366 1.371 1.361 1.361 1.369
C3-C4 1.431 1.441 1.426 1.427 1.444 1.435 1.422 1.443
C2-H6 1.075 1.069 1.074 1.075 1.086 1.079 1.088 1.080
C3-H7 1.077 1.070 1.075 1.076 1.087 1.080 1.089 1.082
C5O1C2 1.06.5 1.07.2 106.6 106.6 106.4 106.8 107.2 106.3
O1C2C3 110.7 110.8 110.5 110.5 110.5 110.5 110.4 110.5
C2C3C4 106.0 105.6 106.2 106.2 106.3 106.0 106.0 106.3
O1C2H6 115.9 116.2 115.7 115.7 115.4 115.8 115.9 115.4
C3C2H6 133.4 132.9 133.8 133.9 134.1 133.7 133.8 134.1
C2C3H7 126.1 126.8 126.2 126.2 126.6 126.5 126.5 126.6
C4C3H7 127.9 127.6 127.6 127.5 127.1 127.5 127.4 127.1
0.66 0.77 0.64 0.87 0.60 0.63 0.52 0.64
cc-pVDZ
HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
1.343 1.361 1.363 1.381 1.364 1.351 1.382
1.343 1.375 1.378 1.376 1.364 1.365 1.373
1.444 1.434 1.436 1.445 1.438 1.425 1.445
1.075 1.086 1.088 1.092 1.086 1.095 1.087
1.077 1.087 1.089 1.094 1.087 1.096 1.088
107.2 106.7 106.8 106.5 106.9 107.2 106.4
110.9 110.8 110.8 110.5 110.6 110.5 110.5
105.5 105.8 105.9 106.2 106.0 105.9 106.3
116.3 115.8 115.8 115.4 115.7 115.8 115.4
132.8 133.4 133.5 134.1 133.8 133.8 134.1
126.7 126.2 126.3 126.5 126.6 126.6 126.5
127.8 127.9 127.9 127.3 127.4 127.5 127.2
0.66 0.64 0.74 0.47 0.51 0.40 0.52
cc-pVTZ
HF
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
1.340 1.379 1.361 1.348 1.380
1.336 1.365 1.354 1.355 1.362
1.441 1.440 1.432 1.418 1.439
1.067 1.081 1.075 1.085 1.075
1.068 1.082 1.076 1.086 1.077
107.2 106.4 106.8 107.2 106.3
110.9 110.4 110.4 110.4 110.4
105.5 106.4 106.2 106.1 106.4
116.4 115.6 115.9 116.1 115.6
132.7 134.0 133.6 133.6 134.0
126.7 126.5 126.5 126.5 126.5
127.7 127.1 127.3 127.4 127.1
0.66 0.60 0.61 0.51 0.63
a
Bond lengths in angstroms and angles in degrees; is the dipole
moment in debye.
b
References 31 and 32.
TABLE 2: Equilibrium Geometry for Thiophene
a
6-31G**
coor-
dinate exptl
b
HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
S1-C2 1.714 1.725 1.714 1.717 1.754 1.736 1.715 1.755
C2dC3 1.369 1.345 1.375 1.376 1.378 1.367 1.368 1.376
C3-C4 1.423 1.437 1.418 1.419 1.437 1.429 1.415 1.437
C2-H6 1.078 1.071 1.077 1.078 1.087 1.081 1.090 1.082
C3-H7 1.080 1.074 1.079 1.080 1.091 1.084 1.093 1.085
C5S1C2 92.1 91.3 92.0 91.9 91.4 91.5 91.1 91.3
S1C2C3 111.5 111.8 111.6 111.6 111.4 111.5 111.3 111.4
C2C3C4 112.5 112.5 112.4 112.4 112.9 112.8 112.6 112.9
S1C2H6 119.8 120.4 120.3 120.2 119.8 120.0 120.1 119.9
C3C2H6 128.7 127.8 128.1 128.2 128.7 128.5 128.6 128.7
C2C3H7 123.2 123.6 123.1 123.2 123.2 123.3 123.2 123.2
C4C3H7 124.3 123.8 124.5 124.4 123.9 124.0 124.2 123.9
(0.52 (
0.04)
0.90 0.45 0.78 0.59 0.62 0.54 0.59
cc-pVDZ
HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
1.729 1.725 1.726 1.756 1.738 1.718 1.757
1.349 1.387 1.388 1.382 1.371 1.372 1.379
1.437 1.426 1.427 1.438 1.431 1.417 1.438
1.078 1.090 1.091 1.095 1.088 1.097 1.089
1.080 1.092 1.093 1.097 1.090 1.099 1.092
91.3 92.0 92.0 91.3 91.5 92.0 91.2
111.8 111.6 111.6 111.5 111.5 111.4 111.5
112.6 112.4 112.4 112.9 112.7 112.6 112.9
120.5 120.3 120.3 119.8 120.1 120.0 119.9
127.7 128.1 128.1 128.7 128.4 128.7 128.7
123.6 123.2 123.1 123.2 123.4 123.2 123.2
123.9 124.5 124.5 123.9 123.9 124.2 123.9
0.79 0.67 0.67 0.39 0.46 0.37 0.43
cc-pVTZ
HF
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
1.718 1.743 1.726 1.704 1.744
1.344 1.374 1.363 1.363 1.371
1.432 1.430 1.423 1.409 1.430
1.069 1.082 1.077 1.087 1.077
1.071 1.086 1.080 1.090 1.080
91.5 91.5 91.7 92.2 91.4
111.7 111.4 111.4 111.3 111.4
112.6 112.9 112.7 112.6 112.9
120.6 119.9 120.2 120.1 120.0
127.7 128.7 128.4 128.6 128.6
123.6 123.3 123.4 123.2 123.3
123.8 123.9 123.9 124.2 123.8
0.81 0.47 0.52 0.43 0.49
a
See corresponding footnote in Table 1.
b
References 31, 32, and
34.
Optimized Geometries and Calculated Frequencies J. Phys. Chem., Vol. 100, No. 37, 1996 15057
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by microwave spectroscopy
31-34
are depicted in Tables 1 and
2, respectively. The atom numbering employed is shown in
Figure 1. By examination of the results in Tables 1 and 2,
several observations can be made. With the exception of the
bond lengths calculated by the LDA method, it is clear that all
the bond lengths determined by the DFT method using the
6-31G** and cc-pVDZ basis sets are overestimated in ac-
cordance with the previous observations.
17-19
The only excep-
tion is the CdC bond length determined with a B3LYP/6-31G**
calculation for thiophene, which is predicted to be only 0.002
too short. Also the bond lengths determined at the MP2/cc-
pVDZ level, fc and full, are overestimated,
4
with the exception
of the O-C bond length for furan, which is calculated to be
only 0.001 too short with the MP2(full) method. In going to
the larger cc-pVTZ basis set, the calculated bond lengths by
the BLYP and BVWN methods are still overestimated, but for
those calculated by the B3LYP method, as well as with the LDA
method for all three basis sets, some are overestimated and some
are underestimated.
For the LDA method, the O-C and C-C bond lengths are
calculated to be about 0.01 too short.
17,19,35
The CdC bond
length is almost exactly predicted by the 6-31G** basis set
17,35
but predicted to be about 0.004 too long by the cc-pVDZ
basis set and 0.006 too short by the cc-pVTZ basis set. The
bond angles calculated by the different DFT methods are close
to each other to within a few tenths of a degree.
20
The largest
difference is for the COC and CSC bond angles by the BVWN
and LDA methods, where the difference is as high as 0.9. The
calculated geometries by the MP2(full) and MP2(fc) methods
are close to each other to within 0.001 in most of the cases
and 0.003 at most for bond lengths and 0.1 at most for bond
angles. The calculated bond lengths at the HF level, as well-
known,
17
are generally underestimated.
Among the seven methods used in this study, Tables 1 and
2, the optimized geometry obtained by the B3LYP method has
the best agreement with the experimental geometry, followed
by the MP2 optimized geometry. The HF optimized geometry
is the worst. The BVWN and BLYP geometries are close to
each other, with the optimized geometry calculated by the
BVWN method being slightly better, but both are worse than
the B3LYP geometry. The optimized geometry calculated by
the LDA method behaves differently from those obtained by
the other methods, but it is generally better than that obtained
by the BVWN method and worse than the B3LYP geometry.
The agreement between the calculated and experimental geom-
etries can then be arranged in the order B3LYP, MP2, LDA,
BVWN, BLYP, then HF.
Hertwig and Koch (HK)
36
calculated the average error for
the difference between the experimental and optimized geom-
etries using the 6-311G* basis set. It was concluded that the
optimized geometries calculated at the DFT/BLYP and DFT/
BP levels are better than those calculated at the HF or MP2
levels. It is clear that the results in the current study for the
two heterocyclic molecules do not support such a conclusion,
although the basis sets used in our study are quite different from
those used by HK. The reason for the difference from HK is
that in the chosen set of molecules there are molecules, for
example F
2
, for which a single reference treatment, such as MP2,
is not expected to yield reasonable results. It is exactly, the
advantage of density functionals, that they are able to treat some
cases for which an explicit multireference treatment would
otherwise be mandatory. One such case is ozone,
37
and another
is the polyene radicals.
38
A detailed discussion of the various
correlation effects in the density functional theory compared to
standard ab initio treatments may be found in the recent work
of Handy and co-workers.
39
Florian and Johnson
11
concluded for formamide that the LDA
and MP2 optimized geometries are comparable to each other.
The results in Tables 1 and 2 for furan and thiophene do not
support this conclusion.
As mentioned above, the B3LYP optimized geometry has
generally the best agreement with the experimental geometry.
The exceptions are the S-C bond length and the CSC bond
angle for thiophene, which are generally poorly predicted by
all the DFT methods and the HF method with the 6-31G** and
cc-pVDZ basis sets. The S-C bond length is calculated to be
0.02-0.04 too long by the BLYP, B3LYP, and BVWN
methods, but with the LDA method it is calculated to be only
a few thousandths of an angstrom too long. The CSC bond
angle is underestimated by 0.6-1.0 by all the DFT methods.
Similar observations were found for thiazole,
40
1,3,4-thiadiazole,
and 1,2,5-thiadiazole
21
at the B3LYP/6-31G** level. The worst
among these molecules is 1,2,5-thiadiazole, where the N-S
bond length is calculated to be 0.033 too long and the NSN
bond angle is underestimated by 1.1. The reflection of the
poor prediction of the S-X bond length and the XSY bond
angle (where X and Y ) C or N) was such that the root-mean-
square (rms) deviations of the calculated frequencies from the
experimental frequencies using the scaled force field for the
sulfur-containing molecules were larger than their oxygen
analogs.
10,21,40
In the case of thiophene at the B3LYP/6-31G**
level, the S-C bond length is calculated to be 0.022 too long
and the CSC bond angle is underestimated by 0.7. On the
other hand, at the MP2(full)/6-31G** level the S-C bond length
is exactly predicted and the CSC bond angle is underestimated
by only 0.1. Also at the MP2(full)/cc-pVDZ level, the S-C
bond length is predicted to be 0.011 too long. Using the
cc-pVTZ basis set, this error by the HF and DFT methods is
reduced.
For furan using the BLYP and BVWN methods, with the
three basis sets, the O-C bond length is calculated to be about
0.020 too long, while the COC bond angle is predicted by a
difference of only 0.2 at most. With the LDA method, the
O-C bond length is calculated to be about 0.011 too short
and the COC bond angle is overestimated by 0.7. But with
the B3LYP method the O-C bond length is predicted within
0.002 and the COC bond angle is overestimated by about
0.4. At the MP2 level, the O-C bond length is calculated
within 0.004 at most and the COC bond angle is overestimated
by 0.3 at most. It is concluded that, although the B3LYP
method generally gives a better prediction of the experimental
geometry than the other DFT methods used in our study, the
Figure 1. Atom numbering and internal coordinates for furan (X )
O) and thiophene (X ) S).
15058 J. Phys. Chem., Vol. 100, No. 37, 1996 El-Azhary and Suter
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MP2 optimized geometry, which is only slightly worse than
the B3LYP optimized geometry, avoids large errors in predicting
some coordinates observed with the B3LYP method.
21,40
The general trend of the bond distances could be compared
to the results of Neumann et al.
39
The DFT methods, especially
the LDA approximation, predict too long bond lengths, similar
to the CASSCF calculations. This could be interpreted as the
effect of the static correlation. The HF method, on the other
hand, normally underestimates the bond lengths. Since B3LYP
uses HF exchange potentials and may be seen as a hybrid HF/
DFT method, the geometries are expected to be a mixture of
HF and pure DFT results. However, this is not necessarily true,
as the example of the C-S bond in thiophene shows.
Finally, we compare the effect of changing the basis set on
the optimized geometries. At the HF level the basis set change
from 6-31G** to cc-pVDZ did not improve the optimized
geometry even with the cc-pVTZ basis set. At the MP2 level
the bond lengths are better predicted by the 6-31G** basis set,
while the bond angles are better predicted by the cc-pVDZ basis
set for furan, but they are similar for thiophene. At the DFT
level, similar to that at the MP2 level, the bond lengths are better
predicted with the 6-31G** basis set, while the agreement
between the calculated and experimental bond angles by both
basis sets is almost similar. With the cc-pVTZ basis set, the
calculated bond lengths are shorter than those calculated by the
other two basis sets.
18,19
Consequently the agreement between
the calculated and experimental bond lengths is significantly
improved with the exception of those calculated by the LDA
method and the CdC bond length with the B3LYP method,
where the agreement became worse. The bond angles are almost
unchanged.
Calculated Frequencies. The calculated frequencies for
furan and thiophene are depicted in Tables 3 and 4, respectively.
For comparison, the experimental frequencies reported for
furan
22
and thiophene
23
are also included in Tables 3 and 4. To
facilitate the comparison between the experimental and calcu-
lated frequencies, the average error for the C-H stretching
modes (
1
,
2
,
12
, and
13
in Tables 3 and 4), in-plane modes
(excluding the C-H stretching modes), out-of-plane modes,
mid-IR modes (all vibrational modes excluding the C-H
stretching modes), and the total average error were calculated.
These are included at the end of Tables 3 and 4. Since the
studied molecules belong to the C
2V
symmetry point group, their
21 fundamental vibrations are classified as 8A
1
+ 3A
2
+ 7B
1
+ 3B
2
.
The calculated frequencies at the HF level are grossly
overestimated, with an average error of about 150 cm
-1
, but
the overestimation decreases as the wavenumber decreases. This
is due to the larger anharmonicity of the higher frequency
modes. The situation is similar with the MP2 calculation except
that the average error of the calculated frequencies from the
experimental frequencies is only about 80-45 cm
-1
depending
on the basis set used and on the molecule. On the other hand,
some of the out-of-plane modes, contrary to the HF calculations,
are underestimated, especially with the 6-31G** basis set for
furan. With the DFT calculations, the average error is signifi-
cantly less than that for the MP2 or HF calculations
11,17-19
mainly because the calculated frequencies for the C-H stretch-
ing modes are closer to the corresponding experimental frequen-
cies
11
and most of the bond lengths calculated with DFT
methods are too long.
For the C-H stretching modes, the overestimation of the
calculated frequencies with DFT is inversely proportional to
the overestimation of the C-H bond lengths. The overestima-
tion of the C-H bond lengths decreases in the order LDA,
BLYP, BVWN, then B3LYP. The overestimation of the
calculated frequencies decreases in the order B3LYP, BVWN,
LDA, and BLYP, with the order of LDA and BLYP reversed.
As an example, for furan with the 6-31G** basis set, the C-H
bond lengths are overestimated by about 0.012, 0.010, 0.005,
and 0.003 , with the LDA, BLYP, BVWN, and B3LYP
methods, respectively. The corresponding average error of the
calculated frequencies is 67, 48, 86, and 130 cm
-1
.
In the mid-IR region, the average errors obtained by the four
DFT methods are close to each other, but the error obtained
with the BVWN method is generally the lowest. This may be
interpreted as an advantage of the BVWN method over the more
popular BLYP method. On the other hand, the highest average
error is obtained by the B3LYP method with the 6-31G** and
cc-pVTZ basis sets, but with the cc-pVDZ basis set, the BLYP
method has the highest average error. It is interesting to notice
that for the out-of-plane modes with the 6-31G** and cc-pVDZ
basis sets the B3LYP method has the lowest average error,
around 10 cm
-1
, which is about half that with the other methods,
but with the cc-pVTZ basis set it is the highest, about 20 cm
-1
.
Also with the 6-31G** basis set, the average error obtained by
the MP2 method in the mid-IR region is about twice that by
the DFT methods, but with the cc-pVDZ basis set the average
error is close to those obtained by the DFT methods.
All calculated frequencies by the B3LYP method are over-
estimated, with the exception of only a few bands for thiophene
with the 6-31G** and cc-pVDZ basis sets, and also the
overestimation decreases gradually with the decrease of wave
length,
41
a behavior similar to that observed at the HF and MP2
levels. On the other hand, the calculated frequencies by the
BLYP method are underestimated except for those correspond-
ing to the C-H stretching modes, which are overestimated by
about 40 cm
-1
and only a few bands for thiophene with the
6-31G** and cc-pVDZ basis sets. As a result, scaling of the
BLYP force fields using one-scale-factor scaling might not
improve the agreement between the calculated and experimental
frequencies as a scale factor close to 1.0 is expected. On the
other hand, scaling of the B3LYP force fields is expected to
significantly improve the agreement between the calculated and
experimental frequencies.
10,21,40
Noting that the optimized geometries by the BVWN and
BLYP methods are close to each other, with the one calculated
by the BVWN method being slightly better, the calculated
frequencies by the BVWN and BLYP methods are similar to
each other except that in the mid-IR region the calculated
frequencies by the BVWN method have a smaller average error
and some bands are overestimated. Also the C-H frequencies
are overestimated by about 80 cm
-1
compared to about 40 cm
-1
with the BLYP method. Those calculated by the LDA method
are similar to those calculated by the B3LYP method except
for the C-H frequencies, which are overestimated by about 60
cm
-1
compared to about 130 cm
-1
by the B3LYP method, and
in the mid-IR region some bands are underestimated. This is
because, compared to the experimental bond lengths, some bond
lengths are calculated to be too long and some are calculated
to be too short, while those calculated by the B3LYP method
are generally too long.
The calculated frequencies at the HF level showed little
dependence on the basis sets used. Those calculated at the MP2
level in the mid-IR region with the cc-pVDZ basis set have an
average error about half that with the 6-31G** basis set, which
is comparable to those obtained with DFT calculations. This
is because the bond lengths calculated with the MP2 and cc-
pVDZ basis set are longer than those calculated with the
Optimized Geometries and Calculated Frequencies J. Phys. Chem., Vol. 100, No. 37, 1996 15059
+ +
+ +
6-31G** basis set. With DFT, the calculated frequencies,
similar to the HF ones, showed little dependence on the basis
set used. In the mid-IR region, the average error of the
calculated frequencies by the B3LYP method are the smallest
with the cc-pVDZ basis set, while those calculated by the LDA
method are the smallest with the cc-pVTZ basis set.
Recently, Nonella et al.
42
used the BP86 method with the
6-31G** basis set to calculate frequencies for p-benzoquinone,
1,4-naphthoquinone, and naphthalene. The corresponding root-
mean-square (rms) deviations, excluding the C-H stretching
modes, are 21, 19, and 16 cm
-1
, respectively. For comparison
with our results, we calculated the average errors for the above
mentioned molecules. These are 15, 14, and 12 cm
-1
, respec-
tively. These average errors are close to those obtained in our
study by the BVWN/6-31G** force fields. In addition, most
of the calculated frequencies by the BP86/6-31G** force fields
for the above mentioned molecules are overestimated. This may
suggest that the BP86 and the BVWN methods behave similarly.
As was concluded before at the MP2/DZP level by Simandris
et al.,
5
the calculated frequencies for furan and thiophene in
this work support the experimental assignment for the d
0
isotopomer for both molecules.
It is worth noting that, although a comparison between the
calculated and experimental IR absorption intensities is not
included in our study, Stephens et al.
13
showed that the
calculated IR absorption and vibrational circular dichroism
spectra for 4-methyl-2-oxetanone by the B3LYP method are in
excellent agreement with the experimental spectra and are
significantly more accurate than those obtained by the LDA,
BLYP, and HF methods. Also, those calculated at the MP2
level are only slightly worse than those calculated by the B3LYP
method.
10,21,40
It was concluded also that the 6-31G* basis set
TABLE 3: Comparison between the Experimental and Calculated Frequencies for Furan
a
6-31G**
sym no exptl
b
HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN sym no exptl
b
HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
A1 1 3167 3463 3379 3375 3217 3298 3233 3256 B1 15 1267 1412 1322 1319 1255 1296 1257 1274
2 3140 3430 3353 3349 3186 3268 3208 3223 16 1180 1322 1268 1266 1159 1220 1229 1160
3 1491 1680 1545 1543 1471 1529 1509 1479 17 1040 1165 1093 1091 1027 1071 1043 1030
4 1384 1549 1462 1459 1379 1430 1416 1387 18 873 961 891 889 862 890 866 868
5 1140 1265 1187 1184 1135 1173 1162 1145 B2 19 838 994 810 804 790 839 796 802
6 1066 1161 1128 1126 1056 1098 1106 1056 20 745 862 756 751 726 762 727 734
7 995 1090 1047 1046 984 1022 1004 988 21 603 659 627 623 601 623 629 600
8 871 1090 885 882 856 886 869 860 error
c
CH 293 213 209 48 130 67 86
A2 9 863 956 812 805 835 880 844 846 in-plane
d
132 54 51 12 33 20 9
10 728 856 705 698 681 729 698 687 out-of-plane 110 29 31 27 10 24 21
11 613 663 577 573 593 614 605 595 mid-IR
e
124 45 44 17 25 21 13
B1 12 3161 3457 3373 3369 3211 3292 3226 3250 total 156 77 75 23 45 30 27
13 3129 3417 3343 3339 3175 3258 3198 3212 SF
f
0.819 0.891 0.894 0.985 0.928 0.963 0.965
14 1556 1768 1620 1617 1552 1614 1588 1560 error
c
25 31 32 24 13 19 28
cc-pVDZ
no. HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN no. HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
1 3457 3345 3334 3204 3285 3226 3244 15 1385 1285 1282 1229 1271 1241 1250
2 3423 3316 3308 3174 3256 3200 3212 16 1305 1250 1250 1143 1204 1207 1144
3 1671 1524 1520 1457 1518 1501 1466 17 1145 1062 1059 1011 1053 1022 1016
4 1534 1433 1430 1364 1415 1403 1374 18 957 880 878 859 887 863 865
5 1249 1168 1164 1120 1159 1158 1130 19 985 829 823 799 846 803 812
6 1156 1119 1116 1050 1090 1091 1050 20 851 762 755 723 758 723 733
7 1073 1022 1021 969 1005 985 976 21 658 630 628 602 622 628 600
8 952 879 875 851 881 863 856 286 176 167 36 117 59 74
9 998 848 843 847 887 851 860 120 32 29 25 20 17 17
10 847 729 719 688 734 702 695 101 13 16 23 12 21 16
11 659 605 599 595 614 606 597 113 25 24 24 17 18 17
12 3450 3337 3327 3198 3278 3218 3238 146 54 51 26 36 26 28
13 3410 3304 3296 3163 3245 3190 3200 0.827 0.912 0.917 0.995 0.938 0.970 0.974
14 1755 1590 1585 1536 1600 1576 1546 20 27 28 27 15 19 30
cc-pVTZ
no HF
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN no HF
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
1 3432 3203 3279 3211 3244 15 1408 1255 1295 1240 1276
2 3401 3174 3251 3187 3213 16 1306 1170 1199 1215 1146
3 1662 1455 1513 1490 1466 17 1156 1015 1062 1034 1017
4 1534 1365 1415 1399 1375 18 960 867 894 874 872
5 1256 1129 1167 1154 1142 19 1000 808 858 818 822
6 1153 1045 1086 1094 1045 20 859 726 762 727 736
7 1078 976 1015 995 980 21 659 604 625 630 603
8 954 859 888 872 863 263 35 112 46 75
9 1012 848 893 861 861 122 20 24 13 14
10 855 693 739 709 700 109 19 18 15 11
11 661 599 618 611 601 117 20 22 14 13
12 3425 3196 3272 3203 3238 145 23 39 20 25
13 3390 3163 3241 3178 3203 0.833 0.993 0.938 0.976 0.971
14 1743 1535 1595 1568 1547 25 24 11 15 27
a
Frequencies are in cm
-1
.
b
Reference 22.
c
Average error in cm
-1
.
d
Excluding CH stretching modes.
e
All vibrational modes excluding CH
stretching modes.
f
Scale factor.
15060 J. Phys. Chem., Vol. 100, No. 37, 1996 El-Azhary and Suter
+ +
+ +
is optimal to reproduce an accurate representation of the IR
absorption spectra with the B3LYP method.
Scale Factors. Table 5 shows the internal coordinate
definition used to convert the Cartesian coordinate force fields
to internal coordinate force fields for furan and thiophene. The
scaling of the force fields was performed as described else-
where.
7,10
Although scaling was performed only for the d
0
isotopomers of furan and thiophene, in a second calculation
scaling was done for all the isotopomers of furan and thiophene
for which the vibrational assignment was reported.
22,23
These
are the d
0
, 2,5-d
2
, 3,4-d
2
, d
4
, 2-d
1
, 3-d
1
, and 2,3,5-d
3
isotopomers
for furan
22
and the d
0
, 2,5-d
2
, 3,4-d
2
, d
4
, 2-d
1
, 3-d
1
, 2,3-d
2
, 2,4-
d
2
, 2,3,5-d
3
, and 2,3,4-d
3
isotopomers for thiophene.
23
The
difference between the scale factors when scaling was done for
the d
0
isotopomers only and that when all the isotopomers were
included was in most of cases not more than 0.005. For
consistency with the unscaled frequencies, the results of scaling
reported here are for the d
0
isotopomers only. The obtained
scale factors and the corresponding average errors are in Tables
3 and 4 for furan and thiophene, respectively.
It is clear that scaling the HF and MP2 force fields
significantly improved the average error, bringing them close
to or even smaller than some of those obtained by the DFT
methods. The average scale factors for the two studied
molecules at the HF and MP2 levels are 0.82 and 0.89 with the
6-31G** basis set and 0.83 and 0.91 with the cc-pVDZ basis
set, respectively. These values are close to those obtained for
similar five-membered heterocyclic molecules with the
6-31G**,
10,21,40
0.80 and 0.90 at the HF and MP2 levels,
respectively. The values of the scale factors with the 6-31G**
basis set correspond to 0.91 and 0.94 at the HF and MP2 levels,
respectively, for frequency scaling. These values are close to
those previously reported,
4,43
0.8929 and 0.9427, at the HF and
MP2 levels, respectively.
TABLE 4: Comparison between the Experimental and Calculated Frequencies for Thiophene
a
6-31G**
sym no. exptl
b
HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN sym no. exptl
b
HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
A1 1 3126 3427 3346 3341 3189 3271 3207 3226 B1 15 1256 1407 1314 1311 1240 1282 1226 1259
2 3098 3390 3312 3308 3144 3229 3168 3181 16 1085 1210 1134 1133 1084 1115 1068 1099
3 1409 1597 1488 1483 1416 1470 1477 1419 17 872 951 912 910 846 876 866 853
4 1360 1530 1436 1433 1360 1407 1374 1373 18 751 808 781 778 713 742 754 711
5 1083 1207 1132 1131 1082 1112 1062 1099 B2 19 867 1029 857 847 833 880 833 845
6 1036 1106 1094 1092 1030 1059 1054 1034 20 712 813 732 726 701 728 700 710
7 839 890 867 883 803 832 856 802 21 452 484 457 453 437 453 458 438
8 608 658 630 628 591 610 609 592 error
c
CH 293 213 209 48 130 67 88
A2 9 898 1053 867 855 877 920 883 888 in-plane
d
118 50 49 14 28 22 17
10 683 804 673 667 647 683 654 655 out-of-plane 104 15 20 21 10 17 14
11 565 618 550 542 555 575 570 556 mid-IR
e
113 38 39 16 22 20 16
B1 12 3125 3425 3343 3338 3187 3269 3205 3224 total 147 71 71 23 43 30 30
13 3098 3376 3299 3294 3131 3215 3155 3167 SF
f
0.819 0.888 0.894 0.980 0.925 0.962 0.964
14 1507 1740 1571 1568 1515 1578 1549 1524 error
c
29 24 26 23 16 21 26
cc-pVDZ
no. HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN no. HF
MP2
full
MP2
fc
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
1 3416 3299 3293 3171 3253 3194 3208 15 1379 1269 1268 1217 1259 1203 1237
2 3382 3272 3266 3133 3218 3162 3170 16 1186 1093 1092 1057 1098 1041 1075
3 1587 1466 1463 1410 1462 1473 1412 17 936 892 890 838 869 858 845
4 1509 1400 1399 1342 1390 1358 1355 18 804 770 769 712 748 753 711
5 1181 1088 1087 1053 1085 1044 1073 19 1012 857 852 834 878 830 848
6 1098 1073 1071 1021 1051 1033 1026 20 800 728 724 695 722 692 705
7 882 872 870 799 835 852 799 21 481 454 452 439 454 457 439
8 653 617 615 590 611 606 591 283 170 164 36 120 62 73
9 1035 890 884 882 921 882 895 103 25 23 24 17 24 17
10 789 675 670 647 683 651 656 92 8 10 15 10 19 13
11 613 564 561 556 576 569 558 99 19 18 21 15 22 16
12 3413 3296 3290 3168 3250 3191 3205 134 47 46 24 34 30 26
13 3367 3258 3252 3120 3204 3149 3157 0.829 0.918 0.914 0.992 0.936 0.972 0.970
14 1724 1537 1535 1502 1563 1538 1511 23 27 26 26 19 26 28
cc-pVTZ
no HF
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN no HF
DFT
BLYP
DFT
B3LYP
DFT
LDA
DFT
BVWN
1 3396 3174 3250 3183 3213 15 1400 1242 1284 1224 1262
2 3359 3132 3211 3146 3171 16 1199 1077 1108 1056 1094
3 1560 1395 1444 1452 1402 17 944 850 880 868 856
4 1518 1350 1397 1362 1363 18 806 717 752 762 715
5 1195 1077 1106 1051 1096 19 1027 842 889 842 857
6 1098 1026 1055 1049 1031 20 808 698 727 695 709
7 885 804 839 858 803 21 488 446 462 465 447
8 654 594 615 612 595 261 38 115 49 76
9 1051 884 929 890 898 110 16 21 19 10
10 800 656 694 662 666 102 15 18 16 6
11 617 562 581 576 564 107 16 20 18 10
12 3393 3172 3247 3180 3211 136 20 38 24 21
13 3344 3119 3197 3134 3157 0.834 0.988 0.935 0.975 0.966
14 1709 1496 1555 1526 1508 27 21 12 18 23
a,c,d,e,f
See corresponding footnote in Table 3.
b
Reference 23.
Optimized Geometries and Calculated Frequencies J. Phys. Chem., Vol. 100, No. 37, 1996 15061
+ +
+ +
At the DFT level, the average error of the B3LYP method is
the lowest, with a significant improvement over that obtained
with the unscaled force field. The average values of the
6-31G** and cc-pVDZ scale factors are 0.93 and 0.94,
respectively. The value of the 6-31G** scale factor is the same
as that reported for the above mentioned molecules,
10,21,40
0.93.
It is then concluded, for this set of five-membered heterocyclic
molecules, that scaling the B3LYP force fields produces more
consistent scale factors than those obtained with the MP2 or
HF force fields. With the BLYP method scale factors of 0.98
and 1.00 are obtained with the 6-31G** and cc-pVDZ basis
sets, respectively, but the average error is similar to or larger
by 1 or 2 cm
-1
than that with the unscaled force fields. This
in fact was expected for reasons that were mentioned above.
Practically, upon scaling, the average error for the C-H
stretching modes improved, but at the expense of the average
error for mid-IR modes, which became worse.
In a separate calculation, the BLYP/6-31G** force field for
furan was scaled using two scale factors, one for the C-H
stretching modes and the other for the mid-IR modes. The
obtained average error for the C-H stretching modes was only
2 cm
-1
, for the mid-IR modes it was 10 cm
-1
, and the total
average error was 9 cm
-1
. The corresponding scale factors are
0.97 and 1.02 for the C-H stretching modes and the mid-IR
modes, respectively. For comparison, the same calculation was
repeated for the B3LYP/6-31G** force field for furan, and the
obtained average errors were 1, 8, and 6 cm
-1
for the C-H
stretching modes, mid-IR modes, and all the modes, respectively.
The corresponding scale factors are 0.92 and 0.95, respectively.
It is clear that the use of a unique scale factor for the C-H
stretching modes improved the average error of the BLYP force
field to be close to that obtained by the B3LYP force field.
This might suggest that a further increase of the number of scale
factors might overcome the difference between the BLYP and
B3LYP force fields. However, Rauhut and Pulay (RP)
20
calculated one-scale-factor and multi-scale-factor scaling by the
BLYP and B3LYP methods using the 6-31G* basis set for 20
molecules. They concluded that even with multi-scale-factor
scaling the B3LYP performs uniformly better than the BLYP.
Notice that the above scale factors for the C-H stretching modes
by the BLYP and B3LYP methods are close to those obtained
by RP,
20
0.977 and 0.920, respectively.
The average scale factors for furan and thiophene by the
B3LYP and BLYP force fields using the 6-31G** basis set are
0.93 and 0.98, respectively. These values are close to those
reported by RP
20
with the B3LYP, 0.928, and BLYP, 0.990,
force fields using the 6-31G* basis set. Recently, Scott et al.
44
reported scale factors of 0.9614 and 0.9945 for frequency scaling
by the B3LYP and BLYP methods, respectively. These
correspond to 0.9890 and 0.9243 for force field scaling. These
values are close to those obtained by us and to those obtained
by RP.
20
On the other hand, there is no scale factor we know for the
force fields calculated by the LDA and BVWN force fields.
Scaling the BVWN force field is similar to scaling the BLYP
force field with values of scale factors of 0.96 and 0.97, obtained
with the 6-31G** and cc-pVDZ basis sets, respectively. Scaling
of the LDA and B3LYP force fields is also similar to scale
factors of 0.96 and 0.97 obtained with the 6-31G** and cc-
pVDZ basis sets, respectively, but the average error is larger
than with the B3LYP force field (but smaller than that with the
BLYP and BVWN force fields) due to the fact that in the mid-
IR region some bands are underestimated and some are
overestimated.
The effect of basis set change on the scale factors was small,
with the scale factors determined by the cc-pVDZ and cc-pVTZ
basis sets close to each other and slightly larger than those
obtained with the 6-31G** basis set.
Conclusion
In the present paper the optimized geometries, frequencies,
and scale factors obtained for furan and thiophene with HF,
LDA, BVWN, BLYP, B3LYP, and MP2 methods using the
6-31G**, cc-pVDZ, and cc-pVTZ basis sets were compared.
The agreement between the calculated and experimental geom-
etries can be arranged in the order B3LYP, MP2, LDA, BVWN,
BLYP, and HF. Although the B3LYP optimized geometry is
slightly better than the MP2 optimized geometry, the MP2
optimized geometry avoids large errors in predicting some
coordinates observed by the B3LYP optimized geometry. The
effect of changing the basis set on the bond angles was minor,
but with the exception of the LDA method, the bond lengths
are better predicted by the cc-pVTZ, followed by the 6-31G**,
then the cc-pVDZ basis sets.
Among the methods used in our study, the calculated
frequencies in the mid-IR region by the BVWN force field have
the lowest average error. Among the four DFT methods, those
frequencies calculated by the B3LYP force field have the highest
average error. This is with the exception of the cc-pVDZ basis
set, where the average error is close to that obtained by the
BVWN method, and the calculated frequencies by the BLYP
force field have the highest average error. The calculated
frequencies by the B3LYP force field are generally overesti-
mated, but those calculated by the BLYP force field are
underestimated, except for those corresponding to the C-H
stretching modes. This is reflected such that scaling by the
B3LYP force field produced the lowest average error, and the
average error obtained by scaling the BLYP force field remained
almost unchanged.
The calculated frequencies by the BVWN force field are
similar to those calculated by the BLYP force field, and those
calculated by the LDA force field are similar to those calculated
by the B3LYP force field. The effect of changing the basis set
on the calculated frequencies and scale factors was minor.
In summary, the present study indicates that scaled B3LYP
force fields are preferred for vibrational analysis, where better
agreement between the calculated and experimental geometries,
frequencies, and intensities is expected. In the case where the
optimized geometry is the main interest, the MP2 method is
more reliable, but at the expense of more computational time.
If unscaled force fields are to be used for the vibrational analysis,
the BVWN force field is the most accurate force field among
the DFT methods used in this study.
TABLE 5: Internal Coordinates for Furan and Thiophene
a
no. mode
b
description
q1, q5 r1, r5 C-X stretch
c
q2, q4 r2, r4 CdC stretch
q3 r3 C-C stretch
q6, q7, q8, q9 r6, r7, r8, r9 C-H stretch
q10 R1 + a(R2 + R5) + b(R3 + R4) ring deformation
q11 (a - b)(R2 - R5) +
(1 - a)(R3 - R4)
ring deformation
q12, q13, q14, q15 1 - 2, 3 - 4,
5 - 6, 7 - 8
CH rocking
q16, q17, q18, q19 6, 7, 8, 9 CH wagging
q20 b(1 + 5) + a(2 + 4) + 3 ring torsion
q21 (a - b)(4 - 2) +
(1 - a)(5 - 1)
ring torsion
a
See Figure 1 for definition of r, R, , and internal coordinates.
b
a ) cos 144 and b ) cos 72. Values of normalization constants
are not given.
c
X ) O for furan and X ) S for thiophene.
15062 J. Phys. Chem., Vol. 100, No. 37, 1996 El-Azhary and Suter
+ +
+ +
Acknowledgment. A.A.E.-A. is grateful to Prof. T. A.
Keiderling of the University of Illinois at Chicago for the use
of the CADPAC program installed on the Department of
Chemistry Titan minisupercomputer. A generous grant of
computer time at the Centro Svizzero di Calcolo Scientifico
(CSCS) in Manno is gratefully acknowledged.
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