Non-Born-Oppenheimer Molecular Dynamics of the Spin-forbidden Reaction O(³P) + CO(X¹Σ⁺) → CO₂(X¹Σ_g⁺)

Author

Ahern W. Jasper
Richard Dawes, Missouri University of Science and TechnologyFollow

Abstract

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.

Recommended Citation

A. W. Jasper and R. Dawes, "Non-Born-Oppenheimer Molecular Dynamics of the Spin-forbidden Reaction O(³P) + CO(X¹Σ⁺) → CO₂(X¹Σ_g⁺)," Journal of Chemical Physics, vol. 139, no. 15, American Institute of Physics (AIP), Oct 2013.

The definitive version is available at https://doi.org/10.1063/1.4825204

Department(s)

Chemistry

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)

0021-9606

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2013, American Institute of Physics (AIP), All rights reserved.

Publication Date

01 Oct 2013