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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0008647· OSTI ID:1802800
 [1];  [2]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Chemical Theory Center; Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst.; OSTI
  2. Univ. of Minnesota, Minneapolis, MN (United States). Chemical Theory Center; Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst.
+ Show Author Affiliations
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.
Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0015997
OSTI ID:
1802800
Alternate ID(s):
OSTI ID: 1635133
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 152; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical bonding
Complete-active space self-consistent field
Coupling strength
Diabatic states
Excitation energies
Perturbation theory
Photodissociation
Potential energy surfaces