23 October 1998

Chemical Physics Letters 295 Ž1998. 447–454

Complete basis set ab initio computational study of unimolecular

decomposition of dimethyl ether
)
Branko S. Jursic
Department of Chemistry, UniÕersity of New Orleans, New Orleans, LA 70148, USA
Received 7 July 1998; in final form 18 August 1998

Abstract

Complete basis set ab initio computational study was performed with the target of elucidating decomposition paths in
dimethyl ether combustion. Several parallel chemical transformations were considered with the determination of activation
barriers, bond dissociation energies, and enthalpies of the reactions. It was determined that the formation of some carbene
intermediates is an energetically unfavorable process, and that the reaction is occurring through C–O bond fusion, hydrogen
radical abstraction, and elimination reaction. The computed values and reaction outcomes were compared to experimental
results and the reliability of this computational approach for the study of combustion chemistry was discussed. q 1998
Published by Elsevier Science B.V. All rights reserved.

1. Introduction chain reaction, the first step includes the formation

One of the alternative fuels that are currently in
consideration is dimethyl ether. Naturally, there is
considerable interest in exploring the decomposition
pathways under combustion conditions. It is known
that thermal decomposition of dimethyl ether is a
first-order reaction w1x that could be explained by a
chain reaction initiated by the C–O bond breaking
w2x. Later, Benson and Jain estimated that the activa-
tion barrier for this reaction should be around 81
kcalrmol w3x. In their studies of the major products
of decomposition, carbon monoxide, methane, and
hydrogen in roughly equimolar amounts with small
amounts of formaldehyde and ethane were isolated.
The formations of formaldehyde and methane were
proposed to be formed from a chain reaction. In this
)
Corresponding author. E-mail: bsjcm@uno.edu
of methoxy and methyl radicals by CH 3 OCH 3 fis-
sion. In the second step, the methyl radical abstracts
the hydrogen radical from dimethyl ether, producing
the CH 3 OCH 2 radical, which later decomposes to
formaldehyde and the methyl radical w3x. In more
recent infrared multiphoton decomposition studies,
Kutschke and coworkers w4x suggest that in its
ground-state dimethyl ether decomposition starts with
the C–O bond breaking w4x. To get more insight into
the dimethyl ether decomposition process, Nash and
Francisco perform the MP2–MP4 ab initio study of
some key intermediates and transition-state struc-
tures w5x. Considering the importance of dimethyl
ether as an alternative fuel, there are a very limited
number of experimental and high-level reliable ab
initio studies. To get more information on dimethyl
ether decomposition pathways we have performed
complete basis set ab initio computational studies of
dimethyl ether decomposition processes.

0009-2614r98r$ - see front matter q 1998 Published by Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 6 1 4 Ž 9 8 . 0 0 9 8 8 - 9
448 B.S. Jursicr Chemical Physics Letters 295 (1998) 447–454

2. Computational methods systems. Therefore, it is reasonable to assume that

All computational studies are performed with the
GAUSSIAN 94 w6x computational package with ab
initio methods as implemented in the computational
package. The complete basis set ŽCBS. method was
developed by Petersson and coworkers w7–10x. The
family name reflects the fundamental tenet underly-
ing these methods, which is the largest error in the
ab initio calculations results from basis set trunca-
tion. The energy of the chemical system is computed
from a series of calculations. The initial calculation
starts with geometry optimization and frequency cal-
culation at the HFr6-31GŽdX . theory level w11x. The
geometry is further optimized at the MP2r6-31GŽdX .
w12–14x theory level with single point energy calcu-
lation at QCISDŽT.r6-31q ŽdX . w15x, MP4ŽSDQ.r
CBSB4 w16x, and MP2rCBSB3. The model also has
empirical corrections for spin contamination and a
size-consistent high-order correction. An explanation
for basis set abbreviation can be found elsewhere
w17x. All energies are computed on fully optimized
structures of anions, cations, and neutral molecules.
3. Results and discussion
The complete basis set ŽCBSQ. ab initio computa-
tional method has been proven in many of our
computational studies to be a highly accurate compu-
tational method for the evaluation of thermodynamic
properties w18–27x, activation barriers w28–30x, and
bond dissociation energies w31x for various chemical
the CBSQ exploring of the potential energy surface
for the decomposition of dimethyl ether should pro-
duce accurate energies and shed light into their
decomposition pathways. The results should be use-
ful for both theoreticians, as well as for experimen-
talists, for the thorough exploration of dimethyl ether
and other ethers’ combustion products and pathways.
As is mentioned above, it was proposed that the
first step in the dimethyl ether decomposition is the
C–O bond breaking. Experimentally, it was esti-
mated that the enthalpy for the C–O bond fission
process is 81.1 kcalrmol w2x. Widely used HF and
MPO2 ab initio methods are not capable of comput-
ing accurate bond dissociation energies. The bond
dissociation energies for dimethyl ether are not an
exception ŽTable 1.. It is necessary to apply a high
level of ab initio methods to obtain an excellent
agreement between computed and experimental val-
ues. In many of our previous computational studies,
we have demonstrated that the CBSQ ab initio
method produces highly reliable energies, and in
some instances experimental values should be cor-
rected w32x. We believe that it is the case for the
C–O bond dissociation energy of dimethyl ether.
The best estimated bond dissociation energy at 0 K
with the CBSQ is 82.4 kcalrmol, which is 1.3
kcalrmol higher than the best estimated bond disso-
ciation energy ŽTable 1.. We believe that the correct
C–O bond dissociation energy is 82.4 kcalrmol.
In dimethyl ether there are also six C–H bonds
that can be broken under combustion, or atmospheric
reaction conditions. As already pointed out in case of

Table 1
Total energies Ža.u.. for dimethyl ether, methoxy and methyl radicals with C–O bond dissociation energy ŽBDE, kcalrmol. for dimethyl
ether
Theory EŽCH 3 OCH 3 . EŽCH 3 O. EŽCH 3 . BDE
X
HFr6-31GŽd . y154.063352 y114.419513 y39.558737 53.4
X
HFr6-31GŽd . Ž0 K. y153.977648 y114.381033 y39.528037 43.0
X
MP2r6-31GŽd . y154.510608 y114.692942 y39.670092 92.6
X
QCISD T r6-31q Žd .
Ž . y154.569829 y114.738939 y39.696843 84.1
MP4rCBSB4 y154.606078 y114.754241 y39.718505 83.7
MP2rCBSB3 y154.709754 y114.825005 y39.730078 97.1
CBS-Q Ž0 K. y154.749773 y114.873304 y39.745166 82.4
CBS-Q y154.744481 y114.869462 y39.740882 84.2
Experimental 81.1

Ž0 K. s sum of electronic and zero-point energies.

 B.S. Jursicr Chemical Physics Letters 295 (1998) 447–454 449

the C–O bond dissociation energy computation, tra-
ditional ab initio methods have a problem in repro-
ducing experimental bond dissociation energies. The
experimental value of 95.5 kcalrmol w33x is quite
well reproduced with the CBSQ ab initio method. It
was estimated at 0 K that the C–H bond dissociation
energy is 95.5 kcalrmol. This energy is very high
and certainly demonstrates that the C–O bond break-
ing is thermally more preferable than the C–H bond
breaking. Formation of the CH 3 OCH 2 radical is
crucial in explaining the formation of formaldehyde
and carbon monoxide as products of dimethyl ether
combustion. Therefore, we have explored another
way for the CH 3 OCH 2 radical formation, which
formation through the methyl radical hydrogen ab-
straction reaction. Enthalpy of the reaction for the
hydrogen radical abstraction is estimated to be y8.0
kcalrmol ŽTable 2., indicating that the CH 3 q
CH 3 OCH 3 ™ CH 4 q CH 3 OCH 2 reaction should be
energetically preferable.
Therefore, it is highly possible that the formation
of the CH 3 OCH 2 radical occurs in the dimethyl
ether combustion. The most reasonable path in the
CH 3 OCH 2 radical decomposition is through the
elimination of formaldehyde. The transition-state
structure computed with the MP2r6-31GŽdX . theory
level is presented in Table 3. The transition-state
structure TS1 represents all characteristics of a clas-
sical transition state. The breaking C–O bond is
extended by approximately 50% of its bond distance
in dimethyl ether, and the C–O–C bond angle is
much wider than in the ether. On the other hand, the
other C–O bond in TS1 has a partially double bond
character ŽTable 3.. The computed formaldehyde
elimination barrier depends on the applied ab initio
theory level. For instance, the MP2 computes sub-
stantially higher activation barriers than QCISDŽT..
The energy that we trust the most is 25.6 kcalrmol,
and it is obtained with CBSQ at 0 K ŽTable 3.. This
activation barrier is very small in comparison to the
initial C–O breaking energy and it has a high proba-
bility of occurring in the process of dimethyl ether
combustion. Furthermore, the enthalpy for the elimi-
nation reaction is only 6.4 kcalrmol, indicating an
energetic preference for this chemical transforma-
tion.
The formation of formaldehyde is energetically
preferable, but it is a final product of decomposition
or a sign that decomposition is continuing. To further
evaluate this problem, we have now explored the
decomposition pathways of formaldehyde. One of
the possibilities is the direct elimination of hydrogen
to produce carbon monoxide. In fact, the reaction is
reversed for the carbene addition to hydrogen. Tran-
sition-state TS2 for this reaction is presented in
Table 4. The symmetry that is present in formal-
dehyde is lost in the transition state. While one C–H
bond distance is extended Ž1.717 A ˚ ., the other hy-
drogen HCO bond angle is distorted in such way that
it comes closer to the other hydrogen by partially
increasing the H–H orbital overlap, which is indi-
cated by the H–H bond distance of 1.344 A ˚ ŽTable
4.. The computed activation barrier for this reaction
is 81.3 kcalrmol ŽTable 4., a value almost identical
to the estimated C–O bond dissociation energy Ž82.4
kcalrmol. in dimethyl ether, which is the initial step

Table 2
Total energies Ža.u.. for methylmethylene ether radical, methane, and hydrogen with estimated C–H bond dissociation energy ŽBDE,
kcalrmol. in dimethyl ether and enthalpy for CH 3 q CH 3 OCH 3 ™ CH 4 q CH 3 OCH 2 reaction ŽEOR, kcalrmol.
Theory EŽCH 3 OCH 2 . EŽCH 4 . EŽH. BDE EOR
X
HFr6-31GŽd . y153.435623 y40.194874 y0.498233 81.3 y5.3
X
HFr6-31GŽd . Ž0 K. y153.364930 y40.147362 y0.498233 71.8 y4.1
X
MP2r6-31GŽd . y153.859251 y40.334358 y0.498233 96.1 y8.1
X
QCISD T r6-31q Žd .
Ž . y153.919311 y40.359955 y0.498233 95.6 y7.9
MP4rCBSB4 y153.946645 y40.389690 y0.498233 101.2 y7.4
MP2rCBSB3 y154.048641 y40.404123 y0.499818 101.2 y8.1
CBS-Q Ž0 K. y154.098174 y40.409583 y0.499818 95.2 y8.0
CBS-Q y154.092827 y40.405771 y0.497457 96.8 y8.3
Experimental 95.5

0 K s sum of electronic and zero-point energies.

450 B.S. Jursicr Chemical Physics Letters 295 (1998) 447–454

Table 3
Total energies Ža.u.. and geometries for transition state of methyl radical elimination from CH 3 OCH 2 radical ŽTS1. with activation barriers
ŽAB, kcalrmol. and enthalpy of reaction ŽEOR, kcalrmol.

Theory EŽTS1. EŽH 2 CO. AB EOR

X
HFr6-31GŽd . y153.385767 y113.866665 31.3 6.4
X
HFr6-31GŽd . Ž0 K. y153.321334 y113.837677 27.4 y0.5
X
MP2r6-31GŽd . y153.797825 y114.175798 38.5 8.4
X
QCISDŽT.r6-31q Žd . y153.874100 y114.209528 28.4 8.1
MP4rCBSB4 y153.892420 y114.215980 34.0 7.6
MP2rCBSB3 y153.984799 y114.300106 40.1 11.6
CBS-Q Ž0 K. y154.057455 y114.342778 25.6 6.4
CBS-Q y154.051734 y114.338967 25.8 8.1

Ž0 K. s sum of electronic and zero-point energies.

for the decomposition process. Therefore, in compar- maldehyde through consecutive hydrogen radical
ison to the C–O bond dissociation energy, direct eliminations. The computed energies for the stepwise
hydrogen elimination from formaldehyde is possible. elimination of two hydrogen radicals from formal-
One can also envision the decomposition of for- dehyde are presented in Table 5. First, the rate

Table 4
Total energies for TS2 singlet and triplet CO and H 2 with activation barrier ŽAB, kcalrmol. for hydrogen molecule elimination from
formaldehyde, enthalpy for the same reaction ŽEOR, kcalrmol., and energy difference Ž D E, kcalrmol. between triplet and singlet carbon
monoxide

EŽTS2. EŽs-CO. EŽt-CO. EŽH 2 . AB EOR DE

A y113.696213 y112.739131 y112.548052 y1.126828 107.0 0.4 120.0
B y113.676801 y112.733573 y112.544071 y1.116243 100.9 y7.6 118.9
C y114.023975 y113.030764 y112.795218 y1.144141 95.3 0.6 147.8
D y114.065065 y113.057782 y112.834785 y1.151648 90.7 0.1 139.9
E y114.071036 y113.047546 y112.817570 y1.166198 91.0 1.4 144.3
F y114.156010 y113.129895 y112.896132 y1.162800 90.4 4.7 146.7
G y114.213212 y113.181486 y112.958971 y1.166085 81.3 y3.0 139.6
H y114.209261 y113.178181 y112.955663 y1.162781 81.4 y1.3 139.6
X X X X
A s HFr6-31GŽd .; B s HFr6-31GŽd .Ž0 K.; C s MP2r6-31GŽd .; D s QCISDŽT.r6-31Gq Žd .; E s MP4rCBSB4; F s MP2rCBSB3;
G s CBS-Q Ž0 K.; H s CBS-Q.
 B.S. Jursicr Chemical Physics Letters 295 (1998) 447–454 451

Table 5 Another way of formaldehyde decomposition is

Total energy for HCO radical and first and second bond dissocia- through H 2 CO rearrangement into HCOH, and then
tion energy in H 2 CO
two hydrogen radical eliminations from HCOH.
Theory EŽHCO. BDE 1 BDE 2
Transition-state structure TS3 for the rearrangement
X
HFr6-31GŽd . y113.248885 75.0 7.2 reaction is a classic transition-state structure. It is
X
HFr6-31GŽd . Ž0 K. y113.234579 65.8 1.7
X triangular with partially broken C–H and partially
MP2r6-31G d .
Ž y113.542487 84.8 8.5
QCISDŽT.r6-31qŽd .
X
y113.573733 86.3 11.1 formed OH bonds ŽTable 6.. The computed activa-
MP4rCBSB4 y113.570571 92.4 15.6 tion barrier is 82.5 kcalrmol at the CBSQ Ž0 K.
MP2rCBSB3 y113.654228 91.7 15.4 theory level. This activation barrier is slightly higher
CBS-Q Ž0 K. y113.704205 87.1 14.4 than the activation barrier for the direct hydrogen
CBS-Q y113.700407 88.5 15.5
elimination, and therefore, it is not energetically
Ž0 K. ssum of electronic and zero-point energies; BDE 1 senergy preferable. The enthalpy of the rearrangement reac-
for H 2 CO™ HCOqH; BDE 2 senergy for HCO™COqH. tion is estimated to be 52.7 kcalrmol. In the HCOOH
rearrangement product, there are two possibilities in
the consecutive hydrogen radical eliminations that
form carbon monoxide. The first step is C–H or
determining step in this transformation is the forma- O–H bond breaking. Second, the hydrogen elimina-
tion of the formyl radical ŽHCO.. The computed tion as we have demonstrated above is occurring
bond dissociation energy is 87.1 kcalrmol, while the with a relatively modest energy requirement. The
second hydrogen radical elimination is occurring C–H bond dissociation energy in HCOH is estimated
with a relatively modest energy requirement Ž14.4 to be 77.0 kcalrmol ŽTable 6.. On the other hand,
kcalrmol.. Considering the fact that the activation HO bond dissociation energy for HCOH is only 34.4
energy for the hydrogen molecule elimination from kcalrmol. If HCOH is formed, the first step is the
formaldehyde is estimated to be 81.3 kcalrmol, this hydrogen radical elimination by O–H bond breaking
process is not present in the formaldehyde decompo- Žonly 34.4 kcalrmol., and then second is the hydro-
sition. gen radical elimination from the HCO radical Žonly

Table 6
Total energies Ža.u.. for TS3, HCOH, and COH radical, the activation barrier ŽAB, kcalrmol. and enthalpy for H 2 CO ™ HCOH
rearrangement ŽER, kcalrmol. with CH ŽBDE 1 , kcalrmol. and OH ŽBDE 2 , kcalrmol. bond dissociation energies for HCOH and enthalpy

Theory EŽTS3. EŽHCOH. EŽCOH. AB ER BDE 1 BDE 2

X
HFr6-31GŽd . y113.696097 y113.782080 y113.189768 107.0 53.1 59.0 21.9
X
HFr6-31GŽd . Ž0 K. y113.674222 y113.753095 y113.174585 102.6 53.1 50.4 12.7
X
MP2r6-31G d .
Ž y114.023912 y114.076022 y113.460395 95.3 62.6 73.7 22.2
X
QCISDŽT.r6-31q Žd . y114.060687 y114.119584 y113.500114 93.4 56.4 76.1 29.9
MP4rCBSB4 y114.073863 y114.132929 y113.504937 89.2 52.1 81.4 40.2
MP2rCBSB3 y114.161143 y114.210624 y113.581215 87.2 56.1 81.3 35.5
CBS-Q Ž0 K. y114.211343 y114.258805 y113.636227 82.5 52.7 77.0 34.4
CBS-Q y114.207364 y114.254968 y113.632424 82.6 52.7 78.5 35.8

Ž0 K. s sum of electronic and zero-point energies.

452 B.S. Jursicr Chemical Physics Letters 295 (1998) 447–454

Table 7
Total energies Ža.u.. for TS4, methanol, and methylene ŽCH 2 . with activation barrier ŽAB, kcalrmol. for methylene elimination from
dimethyl ether and enthalpy for same reaction ŽER, kcalrmol.

Theory EŽTS4. EŽCH 3 OH. EŽCH 2 . AB ER

X
HFr6-31GŽd . y153.896317 y115.032735 y38.874230 104.8 98.1
X
HFr6-31GŽd . Ž0 K. y153.818804 y114.977596 y38.856342 99.7 90.2
X
MP2r6-31GŽd . y154.352846 y115.349760 y38.973748 99.0 117.4
X
QCISD T r6-31q Žd .
Ž . y154.419986 y115.391304 y39.007829 94.0 107.1
MP4rCBSB4 y154.463057 y115.424583 y39.020452 89.7 101.1
MP2rCBSB3 y154.565460 y115.507917 y39.026510 90.5 110.0
CBS-Q Ž0 K. y154.616256 y115.538279 y39.056542 83.8 97.2
CBS-Q y154.610583 y115.534019 y39.052759 84.0 99.0

Ž0 K. s sum of electronic and zero-point energies.

14.4 kcalrmol.. Unfortunately, the rearrangement
activation barrier is higher than the activation barrier
for the hydrogen molecule elimination from formal-
dehyde. The fragmentation and rearrangement reac-
tion of formaldehyde and its isomers have been
extensively studied by experimentalists and theoreti-
cians w34x. Our CBSQ computed energies are in
excellent agreement Ž; 1 kcalrmol deviation. with
coupled-cluster ab initio and some experimental val-
ues w34x.
Although the studied reaction paths perfectly ex-
plain the products of dimethyl ethers, it is reasonable
to explore a few other paths of the decomposition,
notably the decomposition processes that form car-

Table 8
Total energies Ža.u.. for TS5 and CH 3 OCH carbene with activation barrier ŽAB, kcalrmol. for hydrogen elimination from dimethyl ether
and enthalpy for same reaction ŽER, kcalrmol.

Theory EŽTS5. EŽCH 3 OCH. AB ER

X
HFr6-31GŽd . y153.892516 y152.811157 107.2 78.7
X
HFr6-31GŽd .Ž0 K. y153.817014 y152.752080 100.8 68.6
X
MP2r6-31G d .
Ž y154.349645 y153.235883 101.0 81.9
X
QCISDŽT.r6-31q Žd . y154.417506 y153.299062 95.6 74.7
MP4rCBSB4 y154.454757 y153.316194 95.0 77.6
MP2rCBSB3 y154.556089 y153.414789 96.4 82.9
CBS-Q Ž0 K. y154.611833 y153.473119 86.6 69.4
CBS-Q y154.606506 y153.468194 86.6 71.2

0 K s sum of electronic and zero-point energies.

 B.S. Jursicr Chemical Physics Letters 295 (1998) 447–454
benes. At least two processes can be envisioned. One
by the elimination of the carbene with the formation
of stable molecules of methanol, and the other which
eliminates hydrogen and forms the CH 3 OCH car-
bene. Let us first examine the process of the CH 2
carbene elimination ŽTable 7.. The transition-state
structure represents a concerted process of C–H and
C–O bond breaking with the formation of CH 2
carbene. These bond distances, as well as the H–O
bond distance that is very close to the O–H bond
distance in methanol, indicates that the transition-
state structure is very close to the geometry of the
separate products; therefore, the activation barrier
should be very high. It was estimated that the activa-
tion barrier for this reaction is 83.8 kcalrmol, with
the enthalpy of elimination to be 97.2 kcalrmol
ŽTable 7.. That definitively eliminates this elimina-
tion reaction as one of the paths of the dimethyl
ether decomposition. It is also obvious that the for-
mation of the product complexes through hydrogen
bonding exist for the carbene insertion reactions into
such polar bonds, like hydroxyl, and that the activa-
tion barrier for this reaction is very small w34x.
Second, the carbene combustion mechanism is the
hydrogen molecule elimination from dimethyl ether.
The transition-state structure, activation barrier, and
enthalpy for this reaction are presented in Table 8
Again, structural parameters for TS5 are ones that
are expected on the basis of our knowledge about
transition-state structures. The transition-state struc-
ture does not have symmetry and the two C–H
bonds in breaking are not identical Ž1.793 and 1.349
A˚ ., having H–H bond distances that indicate a high
orbital overlap. Also, this transition-state structure is
late and the activation barrier should be very high.
That was confirmed with our computational study.
The activation barrier of 86.6 kcalrmol was esti-
mated at the CBSQ Ž0 K. theory level with the
enthalpy of the reaction being 69.4 kcalrmol.
Clearly, this reaction cannot compete with the ho-
molytic C–O bond breaking as an initial step of
dimethyl ether decomposition process.
4. Conclusion
From the high level of complete basis set ab initio
computational results, we can clearly state that the
453
formation of carbene intermediates through CH 2 or
H 2 elimination from dimethyl ether are energetically
a highly demanding process and should not occur in
dimethyl ether combustion. On the other hand, al-
though high in energy, C–O bond fission should be a
dominant process with the formation of CH 3 and
CH 3 O radicals. The C–H bond breaking with the
formation of CH 3 OCH 2 radical is less preferable.
The highly reactive CH 3 radical then reacts with
CH 3 OCH 3 , producing CH 4 and the CH 3 OCH radi-
cal. Later, with a modest activation barrier it de-
grades to the CH 3 radical and formaldehyde.
Formaldehyde, through hydrogen elimination, pro-
duces carbon monoxide. This computational finding
is in full agreement with the experimentally deter-
mined composition of the dimethyl ether decomposi-
tion products: CH 4 , CO, and H 2 in roughly equimo-
lar amounts, along with a small amount of H 2 CO
and C 2 H 6 Žformed from two CH 3 radicals.. In this
way we have demonstrated a high reliability of the
CBSQ ab initio method for exploring the decomposi-
tion path of small molecular systems, as well as
determining reaction paths in dimethyl ether combus-
tion.
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