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Title: Dynamic mapping of conical intersection seams: A general method for incorporating the geometric phase in adiabatic dynamics in polyatomic systems

The incorporation of the geometric phase in single-state adiabatic dynamics near a conical intersection (CI) seam has so far been restricted to molecular systems with high symmetry or simple model Hamiltonians. This is due to the fact that the ab initio determined derivative coupling (DC) in a multi-dimensional space is not curl-free, thus making its line integral path dependent. In a recent work [C. L. Malbon et al., J. Chem. Phys. 145, 234111 (2016)], we proposed a new and general approach based on an ab initio determined diabatic representation consisting of only two electronic states, in which the DC is completely removable, so that its line integral is path independent in the simply connected domains that exclude the CI seam. Then with the CIs included, the line integral of the single-valued DC can be used to construct the complex geometry-dependent phase needed to exactly eliminate the double-valued character of the real-valued adiabatic electronic wavefunction. This geometry-dependent phase gives rise to a vector potential which, when included in the adiabatic representation, rigorously accounts for the geometric phase in a system with an arbitrary locus of the CI seam and an arbitrary number of internal coordinates. Here, we demonstrate this approach inmore » a three-dimensional treatment of the tunneling facilitated dissociation of the S 1 state of phenol, which is affected by a C s symmetry allowed but otherwise accidental seam of CI. Here, since the space is three-dimensional rather than two-dimensional, the seam is a curve rather than a point. The nodal structure of the ground state vibronic wavefunction is shown to map out the seam of CI.« less
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
  2. Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0015997; CHE-1361121
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC); National Science Foundation (NSF)
Contributing Orgs:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; quantum chemical dynamics; particle symmetry; geometric phases; photodissociation; functional equations; regression analysis; hydrogen bonding; integral calculus; diabatization; potential energy surfaces
OSTI Identifier:
1474044
Alternate Identifier(s):
OSTI ID: 1372945

Xie, Changjian, Malbon, Christopher L., Yarkony, David R., and Guo, Hua. Dynamic mapping of conical intersection seams: A general method for incorporating the geometric phase in adiabatic dynamics in polyatomic systems. United States: N. p., Web. doi:10.1063/1.4990002.
Xie, Changjian, Malbon, Christopher L., Yarkony, David R., & Guo, Hua. Dynamic mapping of conical intersection seams: A general method for incorporating the geometric phase in adiabatic dynamics in polyatomic systems. United States. doi:10.1063/1.4990002.
Xie, Changjian, Malbon, Christopher L., Yarkony, David R., and Guo, Hua. 2017. "Dynamic mapping of conical intersection seams: A general method for incorporating the geometric phase in adiabatic dynamics in polyatomic systems". United States. doi:10.1063/1.4990002. https://www.osti.gov/servlets/purl/1474044.
@article{osti_1474044,
title = {Dynamic mapping of conical intersection seams: A general method for incorporating the geometric phase in adiabatic dynamics in polyatomic systems},
author = {Xie, Changjian and Malbon, Christopher L. and Yarkony, David R. and Guo, Hua},
abstractNote = {The incorporation of the geometric phase in single-state adiabatic dynamics near a conical intersection (CI) seam has so far been restricted to molecular systems with high symmetry or simple model Hamiltonians. This is due to the fact that the ab initio determined derivative coupling (DC) in a multi-dimensional space is not curl-free, thus making its line integral path dependent. In a recent work [C. L. Malbon et al., J. Chem. Phys. 145, 234111 (2016)], we proposed a new and general approach based on an ab initio determined diabatic representation consisting of only two electronic states, in which the DC is completely removable, so that its line integral is path independent in the simply connected domains that exclude the CI seam. Then with the CIs included, the line integral of the single-valued DC can be used to construct the complex geometry-dependent phase needed to exactly eliminate the double-valued character of the real-valued adiabatic electronic wavefunction. This geometry-dependent phase gives rise to a vector potential which, when included in the adiabatic representation, rigorously accounts for the geometric phase in a system with an arbitrary locus of the CI seam and an arbitrary number of internal coordinates. Here, we demonstrate this approach in a three-dimensional treatment of the tunneling facilitated dissociation of the S1 state of phenol, which is affected by a Cs symmetry allowed but otherwise accidental seam of CI. Here, since the space is three-dimensional rather than two-dimensional, the seam is a curve rather than a point. The nodal structure of the ground state vibronic wavefunction is shown to map out the seam of CI.},
doi = {10.1063/1.4990002},
journal = {Journal of Chemical Physics},
number = 4,
volume = 147,
place = {United States},
year = {2017},
month = {7}
}