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Title: Semiglobal diabatic potential energy matrix for the N–H photodissociation of methylamine

Abstract

We constructed an analytic diabatic potential energy matrix (DPEM) that describes the N–H photodissociation of methylamine; the electronic state space includes the ground and first excited singlet states. The input for the fit was calculated by extended multi-state complete active space second-order perturbation theory. The data were diabatized using the dipole–quadrupole diabatization method in which we incorporated a coordinate-dependent weighting scheme for the contribution of the quadrupole moments. Therefore, to make the resulting potential energy surfaces semiglobal, we extended the anchor points reactive potential method, a multiscale approach that assigns the internal coordinates to categories with different levels of computational treatment. Key aspects of the adiabatic potential energy surfaces obtained by diagonalizing the DPEM agree with the available experimental and theoretical data at energies relevant for photochemical studies.

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. Univ. of Minnesota, Minneapolis, MN (United States). Chemical Theory Center; Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst.
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1802800
Alternate Identifier(s):
OSTI ID: 1635133
Grant/Contract Number:  
SC0015997
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 24; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Photodissociation; Complete-active space self-consistent field; Perturbation theory; Excitation energies; Chemical bonding; Potential energy surfaces; Coupling strength; Diabatic states

Citation Formats

Parker, Kelsey A., and Truhlar, Donald G. Semiglobal diabatic potential energy matrix for the N–H photodissociation of methylamine. United States: N. p., 2020. Web. doi:10.1063/5.0008647.
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Parker, Kelsey A., & Truhlar, Donald G. Semiglobal diabatic potential energy matrix for the N–H photodissociation of methylamine. United States. https://doi.org/10.1063/5.0008647
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Parker, Kelsey A., and Truhlar, Donald G. Sun . "Semiglobal diabatic potential energy matrix for the N–H photodissociation of methylamine". United States. https://doi.org/10.1063/5.0008647. https://www.osti.gov/servlets/purl/1802800.
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@article{osti_1802800,
title = {Semiglobal diabatic potential energy matrix for the N–H photodissociation of methylamine},
author = {Parker, Kelsey A. and Truhlar, Donald G.},
abstractNote = {We constructed an analytic diabatic potential energy matrix (DPEM) that describes the N–H photodissociation of methylamine; the electronic state space includes the ground and first excited singlet states. The input for the fit was calculated by extended multi-state complete active space second-order perturbation theory. The data were diabatized using the dipole–quadrupole diabatization method in which we incorporated a coordinate-dependent weighting scheme for the contribution of the quadrupole moments. Therefore, to make the resulting potential energy surfaces semiglobal, we extended the anchor points reactive potential method, a multiscale approach that assigns the internal coordinates to categories with different levels of computational treatment. Key aspects of the adiabatic potential energy surfaces obtained by diagonalizing the DPEM agree with the available experimental and theoretical data at energies relevant for photochemical studies.},
doi = {10.1063/5.0008647},
journal = {Journal of Chemical Physics},
number = 24,
volume = 152,
place = {United States},
year = {Sun Jun 28 00:00:00 EDT 2020},
month = {Sun Jun 28 00:00:00 EDT 2020}
}
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https://doi.org/10.1063/5.0008647
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