Non-Born-Oppenheimer Molecular Dynamics of the Spin-forbidden Reaction O(3P) + CO(X1Σ+) → CO2(X1Σg+)
The lowest-energy singlet (1 1A') and two lowest-energy triplet (1 3A' and 1 3A') electronic states of CO2 are characterized using dynamically weighted multireference configuration interaction (dw-MRCI+Q) electronic structure theory calculations extrapolated to the complete basis set (CBS) limit. Global analytic representations of the dw-MRCI+Q/CBS singlet and triplet surfaces and of their CASSCF/aug-cc-pVQZ spin-orbit coupling surfaces are obtained via the interpolated moving least squares (IMLS) semiautomated surface fitting method. the spin-forbidden kinetics of the title reaction is calculated using the coupled IMLS surfaces and coherent switches with decay of mixing non-Born-Oppenheimer molecular dynamics. the calculated spin-forbidden association rate coefficient (corresponding to the high pressure limit of the rate coefficient) is 7-35 times larger at 1000-5000 K than the rate coefficient used in many detailed chemical models of combustion. a dynamical analysis of the multistate trajectories is presented. the trajectory calculations reveal direct (nonstatistical) and indirect (statistical) spin-forbidden reaction mechanisms and may be used to test the suitability of transition-state-theory-like statistical methods for spin-forbidden kinetics. Specifically, we consider the appropriateness of the "double passage" approximation, of assuming statistical distributions of seam crossings, and of applications of the unified statistical model for spin-forbidden reactions.
A. W. Jasper and R. Dawes, "Non-Born-Oppenheimer Molecular Dynamics of the Spin-forbidden Reaction O(3P) + CO(X1Σ+) → CO2(X1Σg+)," Journal of Chemical Physics, vol. 139, no. 15, American Institute of Physics (AIP), Oct 2013.
The definitive version is available at http://dx.doi.org/10.1063/1.4825204
Keywords and Phrases
Analytic representation; Complete basis set limit; Electronic structure theory; Interpolated moving least-squares; Multi reference configuration interactions; Statistical distribution; Surface fitting method; Trajectory calculations; Carbon dioxide; Electronic structure; Molecular dynamics; Reaction kinetics
International Standard Serial Number (ISSN)
Article - Journal
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