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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4978708· OSTI ID:1465947
ORCiD logo [1]; ORCiD logo [1]
  1. Johns Hopkins Univ., Baltimore, MD (United States). Department of Chemistry
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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.

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
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

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Cited By (3)

Photoinduced C–H bond fission in prototypical organic molecules and radicals journal January 2019
Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 2 2 A (3 s ) Rydberg state journal January 2018
Vibronically and spin-orbit coupled diabatic potentials for X(P) + CH 4 → HX + CH 3 reactions: General theory and application for X(P) = F( 2 P) journal February 2019

Figures / Tables (15)

Table I(p. 4)table Table I
Figure 1(p. 5)figure Figure 1
Table II(p. 5)table Table II
Figure 2(p. 6)figure Figure 2
Table III(p. 6)table Table III
Table IV(p. 7)table Table IV
Table V(p. 7)table Table V
Table VI(p. 8)table Table VI
Table VII(p. 8)table Table VII
Table VIII(p. 8)table Table VIII
Table IX(p. 9)table Table IX
Table X(p. 9)table Table X
Table XI(p. 10)table Table XI
Figure 3(p. 11)figure Figure 3
Figure 4(p. 12)figure Figure 4

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