Bm. Rice et Cf. Chabalowski, AB-INITIO POTENTIAL-ENERGY SURFACE FOR H- EXTENDED BASIS-SETS AND CORRELATION TREATMENT(OCS REACTIONS ), Journal of physical chemistry, 98(38), 1994, pp. 9488-9497
Ab initio calculations are presented for the potential energy surface
(PES) of H + OCS. The two triple-zeta AO basis sets used are the 6-311
+G(2df,2p) and aug-cc-pVTZ. The highest levels of correlation employed
are MP4 and QCISD(T) starting with UHF zeroth-order wave functions. T
here are two major reaction channels on the PES: reaction I is H(S-2)
+ OCS((1) Sigma) --> OH((II)-I-2) + CS((1) Sigma), and reaction II is
H(S-2) + OCS((1) Sigma) --> SH((II)-I-2) + CO((1) Sigma). Multiple pat
hways leading from reactants to (I) and (II) were determined. Results
of this study substantiate findings from an earlier quantum chemical s
tudy using a lower level of theory, including (1) the existence of 12
transition states and six stable four-body intermediates; (2) the qual
itative description of the PES; i.e., geometries, relative barriers, a
nd well depths are similar to those in the earlier study; and (3) the
entrance channel transition states leading to (II) are tight, as sugge
sted by experiment. The results presented here also support the explan
ations of observed product energy distributions for (I) and (II) based
on the earlier ab initio study. An additional transition state connec
ting the cis-HOCS and cis-HSCO minima was located, confirming a previo
us suggestion that reaction II could result from hydrogen migration af
ter HOCS formation. The size of the barrier to hydrogen migration on t
his PES, however, indicates that it is a high-energy reaction. The low
-energy pathway leading to (II) is through direct formation of HSCO. T
he current results show a substantial improvement in the quantitative
agreement with experiment over the previously calculated values. Our b
est calculations predict reaction enthalpies for (I) and (II) to be 57
.3 and -11.5 kcal/mol, respectively, well within the uncertainty of th
e experimental data. The measured activation energy for (II), which in
cludes all dynamic and quantum effects such as tunneling, is 3.9 kcal/
mol, Our best theoretical value for the lowest energy barrier leading
to (II) is 5.7 kcal/mol (including zero-point corrections). We emphasi
ze that corrections due to tunneling are not included in this value.