Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH2OH photodissociation

Malbon, Christopher L.; Yarkony, David R.

doi:10.1063/1.4978708

Title: Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH₂OH photodissociation

Journal Article · 03 April 2017 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.4978708 · OSTI ID:1465947

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Johns Hopkins Univ., Baltimore, MD (United States). Department of Chemistry

In this work, a coupled diabatic state representation, H^d, of the 1, 2, 3 ²A states of CH₂OH suitable for the description of the three channel, three state photodissociation process CH₂OH(1 ²A) + hv → CH₂OH(2, 3 ²A) → CH₂O(X, A) + H, cis-CHOH + H, trans-CHOH + H, is reported. The representation is based on electronic structure data (energies, energy gradients, and derivative couplings) obtained exclusively from multireference configuration interaction single and double excitation wave functions. Diabat shifting is employed to improve the representation’s agreement with accurate experimental energetics. A careful analysis of the numerous minima, saddle points, and conical intersection seams is reported. The computed T₀(3 ²A) ~ 35 220 cm^-1 is in excellent agreement with the experimental estimate of 35 053 cm^-1, and the computed channel dissociation energies, D₀, for CH₂O 9453 (10 160), cis-HCOH 30 310.2 (29 923), and trans-HCOH 28 799 (28 391) cm^-1 are in good accord with the measured values given parenthetically. Lastly, these accurate energetics over a wide range of nuclear configurations strongly support the ability of this H^d to enable quality simulations of nonadiabatic dynamics.

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Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States). Department of Chemistry; Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0015997; AC02-05CH11231

OSTI ID:: 1465947

Alternate ID(s):: OSTI ID: 1497841; OSTI ID: 1986356

Journal Information:: Journal of Chemical Physics, Vol. 146, Issue 13; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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