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Title: Quantum dynamical investigation of the simplest Criegee intermediate CH2OO and its O–O photodissociation channels

Abstract

In this study, 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 (X1A1) and O (1D) fragments. The remaining ~95% of the population remains on repulsive B state and dissociates to H2CO (a3A") and O (3P) 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.

Authors:
 [1];  [1];  [1];  [1]
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  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1598540
Alternate Identifier(s):
OSTI ID: 1420698
Grant/Contract Number:  
FG02-87ER13792; CHE-1150851
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CH2OO; CASSCF; Criegee intermediate; photodissociation dynamics; UV-visible spectroscopy

Citation Formats

Samanta, Kousik, Beames, Joseph M., Lester, Marsha I., and Subotnik, Joseph E. Quantum dynamical investigation of the simplest Criegee intermediate CH2OO and its O–O photodissociation channels. United States: N. p., 2014. Web. doi:10.1063/1.4894746.
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Samanta, Kousik, Beames, Joseph M., Lester, Marsha I., & Subotnik, Joseph E. Quantum dynamical investigation of the simplest Criegee intermediate CH2OO and its O–O photodissociation channels. United States. https://doi.org/10.1063/1.4894746
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Samanta, Kousik, Beames, Joseph M., Lester, Marsha I., and Subotnik, Joseph E. Thu . "Quantum dynamical investigation of the simplest Criegee intermediate CH2OO and its O–O photodissociation channels". United States. https://doi.org/10.1063/1.4894746. https://www.osti.gov/servlets/purl/1598540.
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@article{osti_1598540,
title = {Quantum dynamical investigation of the simplest Criegee intermediate CH2OO and its O–O photodissociation channels},
author = {Samanta, Kousik and Beames, Joseph M. and Lester, Marsha I. and Subotnik, Joseph E.},
abstractNote = {In this study, 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 (X1A1) and O (1D) fragments. The remaining ~95% of the population remains on repulsive B state and dissociates to H2CO (a3A") and O (3P) 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.},
doi = {10.1063/1.4894746},
journal = {Journal of Chemical Physics},
number = 13,
volume = 141,
place = {United States},
year = {Thu Oct 02 00:00:00 EDT 2014},
month = {Thu Oct 02 00:00:00 EDT 2014}
}
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