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Quantum dynamical investigation of the simplest Criegee intermediate CH2OO and its O-O photodissociation channels

Samanta, Kousik, Beames, Joseph M., Lester, Marsha I. and Subotnik, Joseph E. 2014. Quantum dynamical investigation of the simplest Criegee intermediate CH2OO and its O-O photodissociation channels. Journal of Chemical Physics 141 (13) , 134303. 10.1063/1.4894746

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Abstract

The singlet electronic potential energy surfaces for the simplest Criegee intermediate CH2OO are computed over a two-dimensional reduced subspace of coordinates, and utilized to simulate the photo-initiated dynamics on the S2 (B) state leading to dissociation on multiple coupled excited electronic states. The adiabatic electronic potentials are evaluated using dynamically weighted state-averaged complete active space self-consistent field theory. Quasi-diabatic states are constructed from the adiabatic states by maximizing the charge separation between the states. The dissociation dynamics are then simulated on the diabatically coupled excited electronic states. The B ← X electronic transition with large oscillator strength was used to initiate dynamics on the S2 (B) excited singlet state. Diabatic coupling of the B state with other dissociative singlet states results in about 5% of the population evolving to the lowest spin-allowed asymptote, generating H2CO (X (1)A1) and O ((1)D) fragments. The remaining ∼95% of the population remains on repulsive B state and dissociates to H2CO (a (3)A″) and O ((3)P) products associated with a higher asymptotic limit. Due to the dissociative nature of the B state, the simulated electronic absorption spectrum is found to be broad and devoid of any vibrational structure.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Institute of Physics (AIP)
ISSN: 0021-9606
Last Modified: 30 Jan 2020 15:31
URI: http://orca.cf.ac.uk/id/eprint/72850

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