An improved quasi-diabatic representation of the 1, 2, 31 A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates

Zhu, Xiaolei; Malbon, Christopher L.; Yarkony, David R.

doi:10.1063/1.4944091

An improved quasi-diabatic representation of the 1, 2, 3¹ A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates

Journal Article · Thu Mar 31 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4944091· OSTI ID:1599341

^[1]; Malbon, Christopher L. ^[2]; ^[2]

Johns Hopkins Univ., Baltimore, MD (United States); Johns Hopkiins University
Johns Hopkins Univ., Baltimore, MD (United States)

In a previous project we constructed a quasi-diabatic representation, H^d, of the 1, 2, 3¹A adiabatic states of phenol from high level multireference single and double excitation configuration interaction electronic structure data, energies, energy gradients, and derivative couplings. That H^d accurately describes surface minima, saddle points, and also regions of strong nonadiabatic interactions, reproducing the locus of conical intersection seams and the coordinate dependence of the derivative couplings. The present work determines the accuracy of H^d for describing phenol photodissociation. Additionally, we demonstrate that a modest energetic shift of two diabats yields a quantifiably more accurate H^d compared with experimental energetics. The analysis shows that in favorable circumstances it is possible to use single point energies obtained from the most reliable electronic structure methods available, including methods for which the energy gradients and derivative couplings are not available, to improve the quality of a global representation of several coupled potential energy surfaces. Our data indicate an alternative interpretation of kinetic energy release measurements near λ_phot ~ 248 nm.

View Accepted Manuscript (DOE)

Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States); Univ. of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-91ER14189

OSTI ID:: 1599341

Alternate ID(s):: OSTI ID: 1421161
OSTI ID: 22657862

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 144; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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Cited By (6)

Photodissociation of phenol in the adiabatic representation: Tunneling, motions of phenyl ring, and kinetic isotope effects He, Ying; Zhao, Huali; Wang, Wenji International Journal of Quantum Chemistry, Vol. 118, Issue 24 https://doi.org/10.1002/qua.25786	journal	September 2018
Diabatic Hamiltonian construction in van der Waals heterostructure complexes Xie, Yu; Sun, Huijuan; Zheng, Qijing Journal of Materials Chemistry A, Vol. 7, Issue 48 https://doi.org/10.1039/c9ta09434b	journal	January 2019
Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH ₂ OH photodissociation Malbon, Christopher L.; Yarkony, David R. The Journal of Chemical Physics, Vol. 146, Issue 13 https://doi.org/10.1063/1.4978708	journal	April 2017
Accuracy of trajectory surface-hopping methods: Test for a two-dimensional model of the photodissociation of phenol Xie, Weiwei; Domcke, Wolfgang The Journal of Chemical Physics, Vol. 147, Issue 18 https://doi.org/10.1063/1.5006788	journal	November 2017
Excited-state dissociation dynamics of phenol studied by a new time-resolved technique Lin, Yen-Cheng; Lee, Chin; Lee, Shih-Huang The Journal of Chemical Physics, Vol. 148, Issue 7 https://doi.org/10.1063/1.5016059	journal	February 2018
Diabatic Hamiltonian Construction in van der Waals heterostructure complexes Xie, Yu; Sun, Huijuan; Zheng, Qijing arXiv https://doi.org/10.48550/arxiv.1910.05213	preprint	January 2019

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