Academic Journal
Non-Born-Oppenheimer Molecular Dynamics of the Spin-forbidden Reaction O(³P) + CO(X¹Σ⁺) → CO₂(X¹Σ g ⁺)
| العنوان: | Non-Born-Oppenheimer Molecular Dynamics of the Spin-forbidden Reaction O(³P) + CO(X¹Σ⁺) → CO₂(X¹Σ g ⁺) |
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| المؤلفون: | Jasper, Ahern W., Dawes, Richard |
| المصدر: | Chemistry Faculty Research & Creative Works |
| بيانات النشر: | Scholars' Mine |
| سنة النشر: | 2013 |
| المجموعة: | Missouri University of Science and Technology (Missouri S&T): Scholars' Mine |
| مصطلحات موضوعية: | 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, Chemistry |
| الوصف: | 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. |
| نوع الوثيقة: | text |
| اللغة: | unknown |
| Relation: | https://scholarsmine.mst.edu/chem_facwork/2332; https://doi.org/10.1063/1.4825204 |
| DOI: | 10.1063/1.4825204 |
| الاتاحة: | https://scholarsmine.mst.edu/chem_facwork/2332 https://doi.org/10.1063/1.4825204 |
| Rights: | © 2013, American Institute of Physics (AIP), All rights reserved. |
| رقم الانضمام: | edsbas.4C84E6E3 |
| قاعدة البيانات: | BASE |
| DOI: | 10.1063/1.4825204 |
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