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On the incorporation of the geometric phase in general single potential energy surface dynamics: A removable approximation to ab initio data

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4971369· OSTI ID:1465365
 [1];  [2];  [3];  [4]
  1. Johns Hopkins Univ., Baltimore, MD (United States). Department of Chemistry; Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA
  2. Stanford Univ., CA (United States). Dept. of Chemistry
  3. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
  4. Johns Hopkins Univ., Baltimore, MD (United States). Department of Chemistry
+ Show Author Affiliations
For two electronic states coupled by conical intersections, the line integral of the derivative coupling can be used to construct a complex-valued multiplicative phase factor that makes the real-valued adiabatic electronic wave function single-valued, provided that the curl of the derivative coupling is zero. Unfortunately for ab initio determined wave functions, the curl is never rigorously zero. However, when the wave functions are determined from a coupled two diabatic state Hamiltonian Hd (fit to ab initio data), the resulting derivative couplings are by construction curl free, except at points of conical intersection. Here in this work we focus on a recently introduced diabatization scheme that produces the Hd by fitting ab initio determined energies, energy gradients, and derivative couplings to the corresponding Hd determined quantities in a least squares sense, producing a removable approximation to the ab initio determined derivative coupling. This approach and related numerical issues associated with the nonremovable ab initio derivative couplings are illustrated using a full 33-dimensional representation of phenol photodissociation. Finally, the use of this approach to provide a general framework for treating the molecular Aharonov Bohm effect is demonstrated.
Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC)
Grant/Contract Number:
SC0015997
OSTI ID:
1465365
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 145; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Photodissociation of phenol in the adiabatic representation: Tunneling, motions of phenyl ring, and kinetic isotope effects journal September 2018
Topological studies related to molecular systems formed during the Big Bang: H 3 + as an example journal April 2019
Multistate, multichannel coupled diabatic state representations of adiabatic states coupled by conical intersections. CH 2 OH photodissociation journal April 2017
Permutation invariant polynomial neural network approach to fitting potential energy surfaces. IV. Coupled diabatic potential energy matrices journal October 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY