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

Samanta, Kousik, Beames, Joseph M. ORCID: https://orcid.org/0000-0002-5508-8236, 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
ISSN:	0021-9606
Date of Acceptance:	1 August 2014
Last Modified:	10 Dec 2022 02:22
URI:	https://orca.cardiff.ac.uk/id/eprint/72850

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