Title: The DQ and DQΦ electronic structure diabatization methods: Validation for general applications

Abstract

We recently proposed the dipole-quadrupole (DQ) method for transforming adiabatic electronic states to diabatic states by using matrix elements of the dipole and quadrupole operators, and we applied the method to 3-state diabatizations of LiH and phenol. Here in this paper we extend the method to also include the electrostatic potential, and we call the resulting method the DQΦ method, which denotes the dipole–quadrupole–electrostatic-potential diabatization method. The electrostatic potential provides extra flexibility, and the goal of the present work is to test and illustrate the robustness of the methods for producing diabatic potential energy curves that tend to the adiabatic curves away from crossings and avoided crossings and are smooth in regions of crossings and avoided crossings. We illustrate the generality of the methods by an application to LiH with four states and by two-state diabatizations of HCl, (H₂)₂, O₃, and the reaction Li + HF → LiF + H. We find that—if enough states are included—the DQ method does not have a significant dependence on the parameter weighting the quadrupole moment, and a geometryindependent value of 10 a₀ ^-2 is adequate in all cases tested. We also find that the addition of the electrostatic potential improves the diabatic potentialsmore » in some cases and provides an additional property useful for increasing the generality of the method for diabatization.« less

Authors:

Hoyer, Chad E.  ^[1];

• Search DOE PAGES for author "Hoyer, Chad E."
• Search DOE PAGES for ORCID "0000-0003-2597-9502"

Parker, Kelsey ^[1]; Gagliardi, Laura ^[1]; Truhlar, Donald G.  ^[1]

• Search DOE PAGES for author "Truhlar, Donald G."
• Search DOE PAGES for ORCID "0000-0002-7742-7294"

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+ Show Author Affiliations

1. Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst., and Dept. of Chemistry, Chemical Theory Center

Publication Date:

Sat May 21 00:00:00 EDT 2016

Research Org.:

Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1471095

Alternate Identifier(s):

OSTI ID: 1253223

Grant/Contract Number:  

SC0008666

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Chemical Physics

Additional Journal Information:

Journal Volume: 144; Journal Issue: 19; Journal ID: ISSN 0021-9606

Publisher:

American Institute of Physics (AIP)

Country of Publication:

United States

Language:

English

Subject:

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS