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Received December 12, 1985 (Revised Manuscript Received March 27, 1986)
883
B. Cyciobutadiene 719 of acepleiadiene (11) or the hydrocarbon (111). Com-
C. [l.l.l]Propeilane 722
D. Methylenecyciopropene 722
E. Cyciopropenyiidene 723
F. Thiirene 723
VI. Some Predictions of I R Spectra of Unknown 723
Molecules
VII. Compilation of ab Initio Vibrational 726
Calculations
V I I I . Summary 726
I. Introductlon 00 00 00
The synthesis of new compounds and the determi-
nation of their structures is one of the main goals in I II Ill
chemistry. In recent decades various kinds of spec-
troscopy have played a major role in structural deter-
mination. Apart from the direct determination of parison of theoretical spectral data for 1-111 with two
structure by means of X-ray analysis, the most useful available absorption curves showed that the assumed
among these spectroscopies are electronic (ultraviolet zethrene was actually I11 and that a newly synthesized
and visible), vibrational (infrared and Raman), nuclear hydrocarbon was really zethrene.
magnetic resonance, and mass spectrometry. Since the 1960s the development of larger and faster
A full use of experimental spectroscopy for the pur- computers together with elaborate ab initio programs
pose of structure determination requires the availability has allowed the routine computation of theoretical vi-
of a theoretical tool that can provide computed spectral brational spectra for molecules of up to, at present,
data in a completely independent way and with an about ten first-row atoms. During the same period the
accuracy sufficient for a meaningful comparison with availability of low-temperature matrix isolation has
the experimental data. An ideal procedure is the fol- made it possible to isolate highly reactive molecules and
lowing. First record the spectrum of a compound of to obtain their spectra. This technique coupled with
unknown structure. Assign to it one or more plausible the advent of Fourier-transform IR spectroscopy has
structures, and compute theoretical spectra for all these provided a powerful new tool to the experimentalist.
Rudolf Zahradnk was barn 1928 and graduated from th9 Prague
Institute of Technology (1952). I n 1956 he received his C.Sc.
w ee (appoximately equivalent to Ph.D.). and in 1968. the D.Sc.
B. Andes Hess. Jr.. is Professor and Chahman of the Deprmwmt &gee; he then became Assodate Professor Of Charles vntvenny.
of Chemistry a1 Vanderbill University. He was bom h WMngton. At present he is the Head of the Group of Theay of the Chemical
DE, in 1940. received a B.A. (Wllllams College) In 1982. an M.S. Reactivity in J. Heyrovskg Institute of Physical Chemistry and
(Yale) h 1963. and a W.D. (Yale) in 1966 under Professor Kenneth Electrochemistry. Czechoslovak Academy of Sciences. Prague.
B. Wberg. After two years of postdoctoralstudles wiih Professor From 1965 to 1984 he spent several periods as visiting professor
Vkgil BoekelheMe at the University of Oregon. he plned the De- at universities in Wuzburg. Darmstadt. Groningen. Giessen. Basb.
partment of Chemistry at Vanderbin University as an assistant Sandal. Osaka. Erlangen. and Leipzig. I n 1970 he received a NSF
professor in 1968. He spent a year (1973-1974) at the H e y o w (Washington) senior fellowship. I n 1981 he was elected in the
Institute. Czechoslovak Academy of Sciences. Prague wnh Dr. International Academy of Quantum Molecular Sciences. He acts
Rudolf Zahradnik as a National Academy of Sclences Exchange as a member of ediorial boards of Journal of Molecular slrucfure
Scientist. His research interests include the thmry of aromaticity. (THEOCHEM). Reactiviiy and Structure (Springer). and Chemical
ab initio wmputatbn of vibratonal spectra and tkaetkal shdies Reviews, and is a member pf the advisoly board of Theorefica
of organic reaction mechanisms. Chemica Acta. Dr. Zahradnik has authored or coauthored about
300 papers, a number of textbooks. and 7 books. These works
deal mainly wiih molecular orbital theory. theory of chemical re-
activity. and weak intermolecular interactions in chemistry and
biology.
\
Q
- .
For example the highly reactive thiirene was prepared
by the following ~ c h e m e . ~
A
1 L
A. Harmonic Approximatlon
Consider the Schrodinger equation for a polyatomic
molecule with M nuclei and N electrons
c c- rab
@>a a=i j>i i=irjj
where the first term in eq 2 is the kinetic energy op- TABLE I. Harmonic and Anharmonic Vibrational
erator for the nuclei and E,, is the second-order energy Frequencies (cm-') of the HCOOH Molecule Given by ab
Initio SCF 4-31G Calculations"
correction and gives the energy of the nuclear motion.
The potential V(R,...RM)consists of the quadratic terms obsd
frequency, calcd frequency (cm-')
in a power series expansion of E(R l...RM)about the mode cm-' harmonic anharmonic
equilibrium position, OH 3570 3769 3629
CH 2944 3160 3047
c=o 1776 1909 1882
- 1-
1 3M a2E
AXiAXj
2 ij=ldxiaxj
+ ... ( 3 )
co
LHCO
LOCO
LCOH
1105
1387
625
1223
1150
1510
659
1366
1140
1490
653
1347
where X1,
X 2 . . X m are the Cartesian coordinates of the Reference 13.
A4 nuclei. The first term E(X10...X3Mo) adds only a
constant to all allowed E,, and can be ignored for the
purposes of mqst vibrational calculations. Since E is be no nonredundant set of simple internal coordinates.
a minimum at the equilibrium geometry, all All of this is taken care of in the commonly used GF
matrix formulation of the vibrational problem by
Wil~on.~
6. Perturbation Treatment of Anharmonicity
and the second term in eq 3 vanishes. If all terms of Most of the vibrational calculations discussed in
order higher than second are neglected, the potential sections IV-VI and listed in Tables IV and V have used
is a quadratic function of the nuclear displacements AXi the harmonic approximation of eq 4, but in recent years
1 3M there has been progress in the ab initio calculation of
E(X1...X3M) - Fii AXiAXj V(R1...R M ) (4) cubic and quartic force coestants. These are the third
2 lJ'1
and fourth order terms that were dropped from eq 3,
where the force constants Fij are given by and their availability allows the possibility of including
F.. =
z~
-
dxiaxj
a2E I (5)
anharmonicity in ab initio treatments of the vibrational
problem. Prior to 1980 this was rarely done, but one
may anticipate it being done more commonly in the
near future. Perturbation theory yields the following
Equation 4 is known as the harmonic approximation.
In the diatomic case this corresponds to replacing the formula for the anharm0nicity:'O
solid curve of Figure 2 by the parabola shown by the 1 1
dashed line. As can be seen, this approximation may xrr = 16 4ww - 16 C4,2[(8 4 - 3 d ) / ~ s ( 4
8
4 -4 1
be satisfactory for small displacements from the equi- (7)
librium position R120,but it cannot be accurate for large
distortions of the molecule. Equation 7 contains the quadratic, diagonal and sem-
A transformation to mass-weighted coordinates, pi = idiagonal cubic, and diagonal quartic force constants.
(mi)*/2AXi,followed by rotation of the coordinates to The wk are the harmonic frequencies. The quartic
coincide with the principal axes of the quadratic form constant +rm may be estimated easily1' (for stretching
in eq 4, gives an expression for V containing only vibrations) or it may be calculated numerically.
squared terms Equation 7 does not yield anharmonicities of high ac-
1 3M curacy, but it represents the only method suitable for
practical application to polyatomic molecules of arbi-
trary structure. Equation 7 is relatively simple. The
where the Q, are coordinates relative to the principal only complication met in the calculation of xW is that
axes and are called "normal coordinates". As a result the force constants 4- and 4- are derivatives of energy
of these transformations eq 2, which depends on 3M with respect to normal coordinates. They are not
variables, separates into 3M equations, each depending therefore force constants obtained by the differentiation
upon a single Q,. Further, each of these is a harmonic of energy with respect to internal coordinates (J"and
oscillator equation with force constant hi.
For a nonlinear polyatomic molecule there turn out
to be six of the A, with value zero. These correspond
-
F,, in the notation of the next sections). The conver-
sion F 4 may be performed by a rather complicated
nonlinear transformation.12 Alternatively, 4w8may be
to the three translational motions and three rotations obtained from the changes of the energy gradient along
of the entire molecule. The six zero-frequency motions normal coordinates. This way of obtaining 4rrsis con-
can be removed by working in a coordinate system with ceptually simple, but computationally it is not eco-
the origin at the center of mass and rotating with the nomic.
molecule. The remaining 3M - 6 degrees of freedom We have selected two examples of the ab initio cal-
are usually specified by internal coordinates such as culation of anharmonicity by means of eq 7. The fiist13
bond lengths and bond angles. As a result, fewer force is for the formic acid molecule. The level of the ab initio
constants need be evaluated, and those that are evalu- calculations was modest, so only a rather approximate
ated have chemical interpretation. Minor difficulties potential was obtained. From the results presented in
arise because the transforrqation to these coordinates Table I it is seen that the inclusion of anharmonicity
is not linear except in the limit of infinitesimal dis- by means of eq 7 leads to better agreement between
placements, and because in particular cases there may theory and experiment, though the error in the com-
Calculations of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 713
TABLE 11. Vibrational Wavenumbers (cm-’) of the Water Molecule Given by ab Initio Calculations
CI-SDQ,b CEPAC MRCI-SD,d
u1 02 03 expt4 eq 7 var calcn var calcn
0 1 0 1b95 1649 (1670) 1625 1623
0 2 0 3152 3261 3211
1 0 0 3657 3619 (3869) 3714 3667
0 0 1 3756 3753 (3980) 3814 3752
0 3 0 4667 4835 4759
1 1 0 5235 5253 5320
0 1 1 5331 5448 5426
(IFor references to experimental data see quoted theoretical papers. Potential obtained by CI-SDQ calculation^,^^ anharmonicities from
eq 7, harmonic frequencies in parenthesis. CTakenfrom ref 15; potential obtained by CEPA calculation,16vibrational frequencies by a
variation method; the frequencies were read from a figure in ref 15, so the fourth digits in the entires may be uncertain. dTaken from ref
17: potential obtained by MRCI-SD calculation^,^^ vibrational frequencies by a variational method.
.
I
4-31G
I I
Hess et al.
EXPT
cm.'
where the first term on the right hand side is the force
Figure 4. The infrared spectrum of cyclobutadiene compared at the reference geometry. Much of the initial devel-
with results of ab initio calculation^^^ at three levels of sophis-
tication. Intensities were not computed in the MP2 work. opment of this computational method was done by P.
Pulayz6 who is the author of the program TEXASz7
same trends hold for bending modes. Figure 4 shows designed especially for this purpose. One may find all
the example of cyclob~tadiene,~~ where the three cal- information necessary for the effective computation in
culations described as 4-31G, 6-31G*, and MP2/6-31G* papers by Pulay (particularly in ref 11 and 26). We
correspond to the three levels of classification above. restrict ourselves here to noting that the force constants
If one ignores the two C-H stretches at high frequency in eq 8 and 10 should be expressed in symmetrized
which, because of the complexity of the matrix isolation internal coordinates and not in Cartesian coordinates.
spectrum in the C-H region, have not yet been iden- This reduces the cost considerably. The most efficient
use of symmetry coordinates was described by Hehre
tified experimentally, all calculated frequencies are too and co-workersB recently, though the method was used
high in the 4-31G calculation. When the basis is im-
proved to 6-31G* all frequencies, except the second a decade earlier by Pulay.% Cartesian coordinates are
lowest, decrease, but are still too high. Inclusion of used for example in standard runs in the HOND05
electron correlation in MP2/6-31G* lowers the fre- program. This is convenient from the point of view of
quencies still further. preparation of the input data, but the cost is excessive
even with relatively small basis sets.
A calculation of the theoretical spectrum of a poly-
I I I . Computation of I R Spectra atomic molecule as outlined above requires a rather
large amount of computer time and human effort. The
This section gives practical details for the ab initio analytical calculation of force constants might be ex-
calculation of theoretical infrared spectra. Section IIIA pected to lessen this work. The first practical method
discusses the effective computation of quadratic and for the analytical calculation of force constants was
cubic force constants. Section IIIB describes the cal- developed by Pople and c o - ~ o r k e r s and, ~ ~now
~ ~ ~ex-
culation of intensities. The example of the water pressions are available for the third3zand higher de-
molecule, noted in section IIB and summarized in Table rivatives within SCF theory. In spite of this progress,
11, indicates that even the most sophisticated ab initio practical application of these higher derivatives is lim-
calculations are not able to compete in accuracy with ited by the requirement of enormous amounts of disc
high-resolution experiments. In practical applications space. The situation seems to be similar with correlated
one might wish therefore to adopt a strategy in which wave functions. Pople, Krishnan, Schlegel, and Bink-
one does not insist so strictly on the nonempirical na- ley's second-order Merller-Plesset treatmentm contained
ture of calculations. This will be discussed in section the first practical scheme for the analytical computation
IIIC. of the energy gradient for a correlated wave function.
Expressions have been given since33-36for up to
A. Force Constants and Frequencles fourth-order derivatives of energy within the C137and
MCSCF%framework. Efficient algorithms are however
Modern programs for ab initio SCF calculations still lacking, so if one wishes to go beyond the Har-
contain packages for the analytical calculation of the tree-Fock level, a force field of the form
energy gradient or, in some programs, for the analytic
calculation of the quadratic force constants. If quad-
ratic force constants (eq 5) are not computed analyti-
cally by the program, they may be obtained from the
energy gradient using the has to be assumed, and a set of energies fitted to it
Fij x [ fJ. ( 41 = -Ai) - fj(qi = +Ai)]/2Ai numerically (by least-squares). In common applications
the expansion ( 1 1 ) is truncated at the quadratic term
(harmonic approximation).
Calculations of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 715
B. Intensities
DIRECT
((
))
I
2000
I
1600
I
I
1200
I I
600
I
400
merical differentiation. Komornicki and McIver's em .'
method used with a point charge field should also have
application in the calculation of Raman intensities, Figure 6. Comparison of 3-21G computed frequencies and in-
tensities (see text) of ethylene with those of experiment.
though problems with numerical accuracy are expected
to be more severe here than for infrared intensities.
bending force constants. Blom and Altona59@*M965 have
C. Use of Empirical Parameters proposed a much more elaborate scheme of scale fac-
tors. Based on the experimental spectra of ethane,
The computation of the vibrational spectrum of a propane, cyclopropane, ethylene, and dimethy1 ether
polyatomic molecule of even modest size is lengthy, and they proposed scale factors (4-31G basis set) for the
one may be forced to work at the SCF level with a small various types of stretches, bends, torsions, and wags.
basis set. In such a case, one must count on a large In addition they suggested a single scale factor to be
overestimation of calculated vibrational frequencies. applied to all off-diagonal force constants. With these
Several simple (more or less) empirical ways have been scale factors they were able to reproduce experimental
suggested to reduce this error. The first is a proposal spectra with an error of less than 1%. Pulay, Fogarasi,
by S ~ h w e n d e m a nto~ compute
~ force constants at ex- and Boggs@~~~ have proposed a set of standard diagonal
perimental geometry rather than at the minimum en- force constant scale factors for their 4-21G basis set
ergy geometry of the basis set used. This need not based on the spectra of glyoxal, acrolein, butadiene,
n e ~ e s s a r i l ylead
~ ~ *to
~ ~improved values of the force ethylene, formaldehyde, and benzene. Their treatment
constants, though experience shows that it often of the off-diagonal scale factors differed from that of
does.54-57Schwendeman's proposal also shortens the Blom and Altona in that they proposed all off-diagonal
computations since the geometry optimization step is force constants (FJ should be scaled by (CiCj)l12 where
dropped. Ciand Cj are the scale factors for Fii and Fjj. Finally
Pulay and collaborators as well as Blom and Altona Bock, George, and Trachtman have also proposed a set
have suggested that even experimental geometries can of scale factors for the 4-31G basis It is note-
sometimes lead to difficulties due to errors in these worthy that useful results may also be obtained by
geometries. Blom and Altona have therefore proposed applying scaling factors to semiempirical calculations
corrections to be applied to various bond distances and of the CNDO type.70371This is important with treat-
angles obtained theoretically with Pople's 4-31G basis ments of large molecules for which ab initio calculations
Pulay and collaborators have done the same are not feasible. If one insists on a strict nonempirical
for Pulay's 4-21G basis 5et.l' Corrections for additional nature of the treatment, the diagonal force constants
bonds have also been proposed.61 may be recomputed by means of a more sophisticated
It has also been found that basis set and electron approach (using a larger basis set and with the inclusion
correlation effects are more important for diagonal force of electron correlation).
constants than they are for most coupling force con- However, if one computes both frequencies and in-
s t a n t ~A. ~force
~ field given by SCF calculations may tensities we contend that useful results can be obtained
therefore be improved considerably if the diagonal of by computing the spectrum at the optimized geometry
the force constant matrix is replaced by data originating of the basis set used and without employing scale fac-
from some other source. There are several possibilities, tors. This is important to note since for unusual and
and the choice depends on the user's taste. One may reactive molecules the experimental geometry may be
use experimental data obtained in some independent unknown and standard geometry scaling factors would
way for diagonal force constants, or the computed di- not be applicable. In Figure 6 are plotted (from bottom
agonal force constants may be reduced by empirical to top) the experimental IR spectrum of ethylene, its
scaling factors (typical values range from 0.8 to 0.9). To spectrum computed with the 3-21G basis set at the
some extent scaling factors also account empirically for experimental geometry and scaled with the scale fadon
anharmonicity. In the simplest instance Pulay and proposed by Pulay, Fogarasi, and B ~ g g for s ~the~ 4-21G
M e ~ e r ~ 'suggested
"~ a single scaling of 0.9 for all diag- basis set, the unscaled spectrum computed at the ex-
onal stretching force constants and 0.8 for diagonal perimental geometry, and f m d y the unscaled spectrum
Calculatlons of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 717
I I
II MP2/6-31G’
I I1
I1 6-3lG“
I I
I I I II 6-3iG”MP2 I I Il1I I I
I
A i B z A i Bz AI AI AiBiBzBzAlBz BI
I I I // I I I I I
4-31G 3600 3200 2600 )7 2000 1600 1200 600 400
I 1 I
cm .’
I 1
3-21G
I I Figure 8. Comparison of computed IR spectra of cyclopropene
with that of experiment. 6-31G**
reference 76.
and experimental data are from
I I
II
I
EXPT
// I I
I
I
I I I
it was shown that the experimental pattern could be
reproduced without relying on empirical parameters.
As a consequence, the vibrational spectra of molecules
to be discussed in this section were all computed at the
3600 3200 2800 )) 2000 1600 1200 800 400
I I I I I I I I I
STO-3G
.. I I. .I STO-3G
1 I.. .I
I1
6-31G
I ... I. . I
6-31G’
.. I .
I I I I 6-31G’
1. I. .I I
II EXPT - 1 - L 1 I
3600
I
I
3200
I I
2800
EXPT
I
2400
I
2000
I
1600
. I .I
I
. . I
1200
I
800
I
400
3600 3200 2800 2400 2000 1600 1200 800 400
cm”
cm”
Figure 10. Comparison of computed IR spectraa of thiirane with
Figure 9. Comparison of computed IR spectra73of ethylene oxide that of experiment.
with that of experimentam
presented at the bottom of this figure and show a frequencies at the SCF level were all computed to be
somewhat improved agreement with experiment. higher than observed. Hence if the 6-31G* calculation
The IR spectrum of ethylene oxide has been calcu- had not been done, one would have predicted the C-S
lated with the STO-3G, 6-31G and 6-31G* basis sets by stretch be at a considerably lower frequency than was
Hess, Schaad, and P~lavarapu,’~ and these results are actually observed. Finally it is seen that the 6-31G*
compared in Figure 9 with the experimental spectrum spectrum reproduces the experimental pattern very
by Nakanaga.80 In all three cases the vibrational well. The ordering of frequencies is predicted well, and
spectrum was computed at the optimized geometry for the relative intensities are in excellent agreement with
the basis set. Komornicki, Pauzat, and Ellinger81have experiment.
also reported the calculated frequencies of ethylene
oxide with the 4-31G and 6-31G** basis sets, and their
results compare quite favorably with those of the similar
basis sets 6-31G and 6-31G*. It is seen from Figure 9 V. Examples of ApplkatronS
that again the pattern is well reproduced by the 6-31G*
basis set. In the fingerprint region there are three weak We have selected from the literature a few examples
bands near 1150 cm-l that have not been assigned with showing the present possibilities of ab initio calculations
certainty in the experimental spectrum. The computed of vibrational spectra in their application to the iden-
spectrum predicts very nicely three weak bands in this tification of molecular structures. The harmonic ap-
region. Although the calculated pattern of the fre- proximation was assumed in all cases. We have inten-
quencies of the three bands at the lowest frequency is tionally selected calculations made with the simpler
somewhat different from experiment, the relative in- approaches (SCF,small and medium basis sets) since
tensities allowed assignment of these bands with rea- only such calculations are applicable to larger molecules.
sonable certainty; and the computed assignments do
agree with those assigned from experiment. It is seen
that the 6-31G basis is able to reproduce the experi-
mental spectrum reasonably well. However the STO- A. HNO
3G computed spectrum is in very poor agreement with
experiment, both in computed frequencies and relative An early example of the use of a computed IR spec-
intensities. This was not so much the case for ethylene, trum to confirm the reported observation of a reactive
and it may be that the disagreement here is because molecule is Botschwina’s ab initio calculationm on
ethylene oxide is a polar molecule while ethylene is not. HNO. This molecule was observed in the gas phase as
A related molecule is thiirane. An interpretation of early as 1958 by Dalby,84and it was identified primarily
its experimental spectrum has recently been reported by IR spectroscopy. Prior to Botschwina’s work there
along with the calculation of its spectrum with several had been controversy over the fundamental frequencies
basis sets.82 These results are summarized in Figure 10. and force field of HNO. Jacox and Milligan@reported
In this case the STO-3G spectrum reproduces the ex- a matrix IR spectrum of HNO and several isotopic
perimental pattern surprisingly well. The ordering of derivatives in 1973 and proposed two possible sets of
the frequencies is correctly predicted, and even the force constants (see Table 111). This is not a unusual
intensities are reasonably good. It is interesting to note situation since, as mentioned in the introduction, there
that the intermediate basis set (3-21G), while again are usually infinitely many sets of force constants that
reproducing the intensities fairly well, does lead to some can give the observed frequencies. Not only was Bot-
ambiguity in the frequencies. One band is out of order schwina able to reproduce the frequencies of the parent
(C-C stretch), but perhaps more serious is the fact that molecule and five of its isotopic derivatives quite well
the intense C-S stretch is predicted to be at lower as seen in Table 111, but also to show clearly that the
frequency than observed. In the cases discussed so far, correct force field is B and not A.
Calculations of Vibrational Spectra Chemical Reviews, 1986, Vol. 86, No. 4 719
TABLE IV (Continued)
structure type of structure type of
formula or name calcn" typeb ref formula or name calcn" typeb ref
HOSi HSiO 6-31G* v 199 HnP+ PH*+ DZ+P Y 234
6-31G*, MP2 Y 138 Hist SH? 6-31G*, MP2 v 138
CEPA Y, 1 200 H3Si SiH3 3-21G Y 165
6-31G* Y 201 H3Si SiH3 MRD CI Y 235
4-31G FC,I 127 HZCN' HCNH+ 6-31G*, MP2 Y 138
3-21G Y 136 HzLiO+ HzO...Li+ ext Y 236
6-31G* Y 201 HZNZ HNNH CI Y 237
6-31G* Y 201 HZNZ HNNH ST03G, 4-31G Y, 1 238
3-21G, 3-21G*, Y 189 HzNz HNNH 6-31G*, MP2 Y 122, 138
6-31G* HZOZ HZOZ 4-31G Y, 1 239
STO-4G I 202 Hz02 HZ02 6-31G*, MP2 Y 122, 138
TZ+P v 203 HzOz HZ02 DZ FC 240
DZ+P Y 204 HzOSi HzOSi CI, CEPA Y 241
DZ v 205 HzOSi HzSiO 6-31G* Y 199
4-21G FC, I 11 HzOSi HSiOH 6-31G* Y 199
6-31G*, MP2 Y 122. 138 H2Sz HzSz 3-21G*, 6-31G* Y 189
6-31G*, MP2 Y 122' HCLiN+ HCN Li+... DZ,EFV Y, 1 242
3-21G Y 206 HCOz HCOZ 6-31G*, MP2 Y 138
DZ FC 126 HNOz HONO ext Y 243
DZ+P/CEPA Y, 1 207 HNOS HNSO ST03G*, 3-21G*, Y 244
SCEP, CEPA Y, 1 143 6-31G*, MP2, MP3
STO-NG,N-31G I 141 Li202 LizOz DZ+P Y 245
DZ FC 208 Nz02 (Noh DZ Y 246
3-21G, 6-31G* Y 209 NzOz (NO), 4-31G Y 247
3-21G, 6-31G* Y 209 N2OS ONNS 4-31G Y 247
DZ Y 210 NZSZ SZNZ CEPA Y 248
3-21G, 3-21G* Y, 1 211 03s so3 3-21G, 3-21G*, 6-31G* Y 189
6-31G, 6-31G* 4CHz ~ZCHZ DZ, DZ+P Y 249
ext Y, 1 212 AlBr3H3N H3N:AlBr, STO3G Y 250
3-21G, 3-21G* Y 189 AlC13HSN HsNAlC13 ST03G Y 250
STOIG, DZ I 213 AlF3H3N H3NAlF3 ST03G Y 250
DZ FC 171 B2H6 HZBHZBHZ 4-31G FC 251
3-21G Y 136 BZH6 HzBHzBHz 4-31G Y 252
ST03G, DZ I 213 BZH6 HZBHZBHZ 6-31G*, MP2 Y 122, 138
3-21G Y 165 B203 OBOBO DZ+P Y, 1 253
ext/CEPA Y 214 BH4- BHc DZ Y 254
DZ+P Y 215 BeF3Li LiBeF, DZ Y, 1 255
DZ+P, CI Y 216 c302 C3OZ 6-31G* Y 256
DZ FC 217 c2L1Z04 LizCz04 3-21G Y 209
3-21G Y 165 CC13N CINCClz DZ Y 257
DZ Y 218 CFHzN HCN HF ... 4-31G Y 128
DZ FC 217 CH3NOZ C 0z... NH, DZ Y 258
4-31G. EFV I 219 CHZNZ HzNCN 4-31G, 4-31G* Y, 1 259
3-21G Y 165 CHzNz HZNNC 4-31G, 4-31G* Y, 1 259
DZ Y 220 CHzCO3 HZC03 4-31G Y 260
min Y 221 CLizOz LizCOz 3-21G Y 209
ext FC 222 CNa2OZ NazCOz 3-21G Y 209
STOBG, 4-31G FC 54 CHOc HCOc 4-31G Y 260
4-21G FC, I 11 F6P PF5 3-21G, 3-21G* Y 189
STO3G I 223 F6P PF6 DZ Y 261
HF limit FC 224 F4Si SiF4 3-21G Y 165
4-31G* Y 225 F3H3 DZ+P, CI Y 216
DZ I 226 F,HSi HSiF3 3-21G Y 165
ST03G, 3-21G, Y 183 FzHzSi HzSiFz 3-21G Y 165
4-21G, 6-21G FH30 Hz0...HF 6-31G Y 262
STOIG, DZ I 213 FH,O HzO HF... TZ+P Y 263
6-31G*, MP2 Y 122, 138 FH30 HZO HF... CSID Y 264
3-21G, 6-31G* Y 136 FH3Si SiH3F 3-21G Y 192
DZ+P I 49 FH3Si SiH3F 3-21G Y 165
6-31G** Y 227 H9+ H*+ CISD Y 178
CISD Y 57, 228 H7+ H,+ CISD Y 178
CI Y 229 H5+ HE.+ CISD Y 178
SCEP,CEPA Y, 1 230 H6P PH5 CEPA FC 233
est Y, 1 231 H4Nt NH4+ 6-31G** Y, 1 75
CISD Y 232 H,N+ NH4+ 6-31G*, MP2 Y 138
DZ+P Y 168 H4N+ NH4+ CISD Y 139
6-31G*, MP2 Y 138 H4NZ HzNNHz STOBG, 4-31G, Y 265
STOIG, 4-31G FC 54 4-31G*, 6-31G*, CI
STOBG, 3-21G, Y 191 H4°Z HZNNHZ 6-31G*, MP2 Y 122,138
4-31G, 6-21G H40Z (HzO)z 4-31G, 6-31G* Y 266
3-21G, 3-21G* v 189 H4°Z (Hz0)~ CI Y 267
CEPA FC 233 H4°Z (Hz0)z 4-31G FC, I 268
ST03G, DZ I 213 H4OZ (HzO)z 4-31G I 269
DZ+P Y 234 HiOz (HzO)z DZ+P Y, I 270
6-31G*, Mp2 Y 138 H4°Z 4-31G u,I 271
3-21G, 6-31G* Y 190 H4°Z (H@)z 4-31G Y 272
722 Chemical Revlews, 1988, Vol. 88, No. 4 Hess et al.
TABLE IV (Continued)
structure type of structure type of
formula or name calcn" typeb ref formula or name calcna typeb ref
H4O2Li+ (H20)2Li+ 4-31G FC, I 268 H4Si2 disilene DZ, DZ+P U 275
H,O2Siz (H2Si0)2 3-21G U 273 H3N3 triaziridine 6-31G*, MP2 u, I 276
HIP+ H,P+ 6-31G*, MP2 u 138 H3N3 triazine 6-31G*, MP2 u, I 276
H4SzSiz (HzSiS)z 3-21G U 273 H3N0 HONHz 4-31G u, I 277
H,Si SiH, ST03G, 4-31G FC 54 H,NO HONHz 6-31G*, MP2 U 122, 138
H,Si SiH, 6-31G*, MP2 u 138 H3N0 HONHz DZ FC 240
H,Si SiH4 3-21G, 3-21G* u 189 H3N0 HONHz STOSG, 4-31G V, I 278
H4Si SiH4 3-21G, 6-31G* u 190 4-31G
H4Si SiH, DZ, DZ+P U 274 H2N20 HzN=NO 4-31G u, I 279
H4Si SiH, 6-31G** u, I 75 H2N20 HN=NOH 4-31G u, I 279
H,Si SiH, 3-21G Y 165 HzO, (HOz)z DZ+P U 197
"DZ means generally a true double-zeta basis set. It may also mean a valence-shell DZ set or a medium-sized basis set of a quality
somewhat better than DZ. u:frequencies computed. FC: force constants reported only. I: intensities comDuted (IR and/or Raman).
I I I I I I I I I
I I
6-31G'
- I. I. .I.
6-31G'
I I . I . . ..I I I .
II
EXPT
I I1 1,
I I I I I I I I I
I600 3200 2800 2400 2000 1600 1200 800 400
cm"
I I I (( I I 1 I I
3600 3200 2800 2000 1600 1200 800 400
Figure 12. Comparison of computed IR spectralo3of I1.1.11- cm"
propellane with that of experiment.lo2
Figure 13. Comparison of computed IR s ectralM of methyle-
necyclopropene with that of experiment. 18
sponding 13Cz-cyclobutadienemixture. The observed
and computed spectra are in good agreement. In the
computed spectrumz5there are six bands below 1700 and co-workers were able to assign the fundamentals
cm-' of relative intensity greater than 0.01. Michl et in the IR and Raman spectra.
al. observed six bands in this region which correspond
well with those computed. A t high frequency a broad D. Methylenecyclopropene
band is observed at 3049 cm-'. calculation^^^ predict
five weak C-H stretches within an 18-cm-' region and The recent synthesis of methylenecyclopropene
a sixth of very weak intensity at somewhat higher fre- (IX)'04J05was confirmed in part by its IR spectrum.lo4
quency. Billups reported five bands which he assigned to the
spectrum of IX. However, while the computed spec-
C. [1.1.1]Propellane
Wiberg and Walker reported in 1982 the synthesis
and IR spectrum of the highly strained but remarkably
stable hydrocarbon [l.l.l]propellane (VIII).102 An
D= IX
I 1 I I I I I I I I
4-31 G
I I. I I.
.I
6-31G'
I I.. I
I. I.
EXPT
.I ClSD I .I
A XI
TABLE V (Continued)
structure type of structure type of
formula or name calcn" typeb ref formula or name calcna typeb ref
HCCH 3-21G,6-31G* Y 136 CzH& HOCHSHqOH DZ Y 355
HCCH DZ+P Y, I 340 C,HnS+ 3-21G Y 324
HCCH DZ+P, CEPA 134 CH;SCH3+- 3-21G Y 324
H&=C CISD 341 HCCCO+ 3-21G, 6-31G* Y 356
H2C=C CI, TZ+P 338 HCCCN DZ+P, CEPA Y 134
HFC=CFH DZ 342 HCCCN DZ+P Y 142
HFC=CFH 3-21G 136 HCCCP DZ+P Y 142
HzNCN 6-31G* 291 cyclopropenylidene DZ, DZ+P Y 78
CH2=C=0 STO3G 290 TCSCF/DZ,
oxirene 3-21G 113 DZ+P
glyoxal DZ 68 HCCCHO CI/DZ+P Y 351
glyoxal 4-31G 66 cyclopropenyl rad. MCSCFI3-21G Y 358
thiirene 4-31G 112 cyclopropene 4-31G Y 58
thiirene 3-21G 113 cyclopropene 6-31G** Y, I 16
vinyl 6-31G**, GVB 343 cyclopropene 6-31G*, MP2 Y, I I9
CHZ=CH+ 6-31G*, MP2 138 cyclopropene DZ+P Y, I 18
H,C=CHF 3-21G 345 CHzCCHz 3-21G Y 136
HZNCCH 6-31G* 291 CHzCCHz 6-31G* Y 291
CH3CN 3-21G 136 CH3CCH 3-21G Y 136
CHaCN 4-31G* 346 CHSCCH 6-31G* Y 291
CH3CN 6-31G* 291 HCCCHzNH2 4-31G(N*) Y, I 359, 360
CH3NC 3-21G 136 CHZ=CHCHO DZ, 4-31G Y 69
azirene 3-21G 113 CHz=CHCHO 3-21G Y 136
HzC=CH2 3-21G, 6-31G* 136 CH,=CHCHO 4-31G Y, I 66
H&=CH2 DZ 63,342 malonaldehyde DZ+P Y 361
HZC=CH2 6-31G*, MP2 30, 122, CHZ=CHCH, 3-21G/ v 362
133 MCHF
HZC=CH2 6-31G* 138 cyclopropyl radical 4-31G Y 363
H2C=CH2 4-31G 327 CHSCHZCN 3-21G Y 136
HZC=CHz 6-31G** 15 CH3CH=CH2 4-31G Y 60
H2C=CH2 DZ+P 194 CH&H=CHz 3-21G, MCHF Y 362
H2C=CH2 ext 339 cyclopropane 4-31G Y 58, 59,
HZC=CH2 4-31G 64,66 363
HZC=CH2 ST04G 98 cyclopropane 3-21G Y 136
H2C=CHp DZ+P 40 cyclopropane ST03G, 4-31G, Y 81
H2C=CH2 ST03G, 6-31G* 106 6-31G**
H2CUH2 3-21G 345 CHzCHzCHz MCSCF/DZ Y 364
2,4-diboramethyl- DZ 347 CH2CH2CHZ DZ Y 365
enecyclopropane CHaCHZCHO 4-21G Y, I 366
CH3CHF 3-21G 345 oxetane 4-21G Y, I 361
oxirane ST03G, 4-31G, 81 acetone 3-21G Y 136
6-31G** epoxypropane 6-31G* Y, I 368
oxirane 6-31G* 13 epoxypropane 4-31G Y, I 12
oxirane 4-31G 12 methylthirane 6-31G Y, I 369
oxirane 3-21G 136 CH3CONHCH3 4-31G Y 370
CHBCHO 4-31G, 6-31G** 348 CHSCONHCH3 ST03G, I 371
CHSCHO 3-21G 136 3-21G
HCOOCHI 3-21G 136 CHSCH2CHs 4-31G Y 58,59
CH3COOH 3-21G 136 CH,CH?CH, 6-31G*, MP2 Y 133
(HzC0)z 3-21G 213 CH~=SI(CH~)~ 4-31G v, I 372
(HCOOH)2 ST03G, DZ 301 (HzC=NOH)S ST03G Y 320
H2C=CHSH 4-31G 349 tetralithio- STOIG, 4-31G/ Y 373
thiirane 6-31G* 82 tetrahedrane 5-21G(Li)
CH3CH2 3-21G 345 HCCCCH DZ+P Y, I 374
CH3CH2 4-21G 350 HCCCCH 3-21G Y 136
CH3CH2' 6-31G*, MP2 138 cyclobutadiene ST04G Y, I 98, 100
CH3CH2F 3-21G 136 cyclobutadiene 6-31G*, MP2 Y, I 25
aziridine STOIG, 4-31G, 81 cyclobutadiene DZ+P Y, I 95
6-31G* tetrahedrane 6-31G*, MP2 u,I 114
aziridine 3-21G, 6-31G** 136 bicyclobutene 6-31G*, MP2 u,I 115
CH,CH=NH DZ 351 methylenecyclopropene 6-31G* Y, I 106
CH,CN=CHZ DZ 351 methylenecyclopropene 6-31G*, MP2 Y I9
HCONHCHa 4-31G, 4-31G* 352 cyclobutyne DZ, DZ+P Y 315
CHSCH3 DZ 63 uracil STO3G Y 316
CHSCH, 4-31G 353 uracil 4-31G Y, I 311
CH3CH3 4-31G 58, 59, CH&CCHO DZ Y 351
354 1,3-butadiene 4-31G Y 318
3-21G 59 1,3-butadiene DZ+P Y 319
6-31G*, MP2 122 1,3-butadiene 4-31G Y, I 66
6-31G* 138 1,3-butadiene 3-21G Y 136
4-31G 321 CH3CCCHB 3-21G Y 136
6-31G** 15 cyclobutane 4-21G Y, I 380
(HsC=NOH), STO3G 320 butane 6-31G Y 381
CHaOCH, 4-31G 65 lithium DZ, DZ+P FC 382
3-21G Y 136 cyclopentadienide
6-31G*, MP2 Y 133 C5H5N pyridine 4-31G Y, I 383
726 Chemical Reviews, 1986, Voi. 86, No. 4 Hess et al.
TABLE V (Continued)
structure type of structure type of
formula or name calcna typeb ref formula or name calcn" typeb ref
C5H5N pyridine 4-21G Y, I 384 CsH, benzene 4-21G u, I 67
C5H5N,0 guanine STO3G Y 385 C6H5 triprismane 4-21G u, I 388
C6H5 [ l.l.l]propellane 6-31G* u,I 103 C8H8 cubane DZ Y 389
C5H,0 CH2=CHCOCH=CH2 4-31G FC 386 CsH8 cubane DZ Y, I 390
C5N30- (NC)2C=C(CN)O- ST03G Y 387 CloH8 naphthalene 4-21G Y, I 391
CBN4 (NC)&=C(CN)Z STO3G Y 387 C,H, polyacetylene ST03G, 4-31G Y 392
"DZ means generally a true double-zeta basis set. It may also mean a valence-shell DZ set or a medium-sized basis set of a quality
somewhat better than DZ. *Y: frequencies computed. FC: force constants reported only. I: intensities computed (IR and/or Raman).
II MP2
I l I II I I
AiBz BzAiAqB,BzAiB, By Ai
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