An ab initio CASSCF study of the Ho + NOCl reaction
- Univ. of Sevilla (Spain)
A theoretical open-shell study of the chlorine abstraction process occurring in the reaction between hydroxyl radical and nitrosyl chloride has been carried out. Fully optimized geometries were obtained from complete active space multiconfigurational self-consistent-field (CASSCF) calculations using the standard 6-31G(*) basis set. Three stationary points on the potential energy hypersurface were located. The reaction occurs via formation of a reactive complex previous to a transition state at a slightly lower energy than reactants. The third stationary point was found between the transition state and products. Energetics of reaction and barrier height have been computed form MR-CISD+Q calculations. The process appears to occur in a plane with an activation energy of 3.6 kcal mol{sup {minus}1} and a reaction enthalpy of {Delta}H{degrees} {sub 298} = -15.3 kcal mol{sup {minus}1}, in agreement with experiment (2.25 and -18.2 kcal mol{sup {minus}1}). The kinetic analysis is coherent with a bimolecular homolytic substitution (S{sub H}2), and a reaction profile fairly similar to that proposed for the S{sub N}2 mechanism is suggested. 25 refs., 3 figs., 3 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 255254
- Journal Information:
- Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 5 Vol. 96; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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