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

Abstract

A coupled diabatic state representation, Hd, 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. These accurate energetics over a wide range of nuclear configurations strongly support the ability of this Hd to enable quality simulations of nonadiabatic dynamics.

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. Johns Hopkins Univ., Baltimore, MD (United States). Department of Chemistry
Publication Date:
Research Org.:
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 Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1465947
Alternate Identifier(s):
OSTI ID: 1497841; OSTI ID: 1986356
Grant/Contract Number:  
SC0015997; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; 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; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Malbon, Christopher L., and Yarkony, David R.. Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH2OH photodissociation. United States: N. p., 2017. Web. doi:10.1063/1.4978708.
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Malbon, Christopher L., & Yarkony, David R.. Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH2OH photodissociation. United States. https://doi.org/10.1063/1.4978708
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Malbon, Christopher L., and Yarkony, David R.. Mon . "Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH2OH photodissociation". United States. https://doi.org/10.1063/1.4978708. https://www.osti.gov/servlets/purl/1465947.
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@article{osti_1465947,
title = {Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH2OH photodissociation},
author = {Malbon, Christopher L. and Yarkony, David R.},
abstractNote = {A coupled diabatic state representation, Hd, 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. These accurate energetics over a wide range of nuclear configurations strongly support the ability of this Hd to enable quality simulations of nonadiabatic dynamics.},
doi = {10.1063/1.4978708},
journal = {Journal of Chemical Physics},
number = 13,
volume = 146,
place = {United States},
year = {2017},
month = {4}
}
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https://doi.org/10.1063/1.4978708
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Cited by: 15 works
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Figures / Tables:

Table I Table I: Generic elementary functions comprising g(i).
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    Works referencing / citing this record:

    Photoinduced C–H bond fission in prototypical organic molecules and radicals
    journal, January 2019

    • Ashfold, Michael N. R.; Ingle, Rebecca A.; Karsili, Tolga N. V.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 26
    • DOI: 10.1039/c8cp07454b

    Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 2 2 A (3 s ) Rydberg state
    journal, January 2018

    • Xie, Changjian; Guo, Hua
    • The Journal of Chemical Physics, Vol. 148, Issue 4
    • DOI: 10.1063/1.5017737
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      Table I (p. 4)table
      Figure 1 (p. 5)figure
      Table II (p. 5)table
      Figure 2 (p. 6)figure
      Table III (p. 6)table
      Table IV (p. 7)table
      Table V (p. 7)table
      Table VI (p. 8)table
      Table VII (p. 8)table
      Table VIII (p. 8)table
      Table IX (p. 9)table
      Table X (p. 9)table
      Table XI (p. 10)table
      Figure 3 (p. 11)figure
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