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Title: Polarizable Mixed Hamiltonian Model of Electronic Structure for Micro-solvated Excited States. I. Energy and Gradients Formulation and Application to Formaldehyde (1A2).

Abstract

We describe an efficient implementation of a polarizable mixed Hamiltonian model of electronic structure that combines Hartree-Fock , Kohn-Sham, or multiconfiguration quantum chemical wavefunctions with a polarizable and flexible molecular mechanics potential of water, and that is applicable to micro-solvated electronic excited states. We adopt a direct algorithm for the calculation of the polarization response of the solvent subsystem. The strategy facilitates the calculation of the energy of the system and of the forces with respect to the solute coordinates and the solvent coordinates, including for excited states. This capability opens the way to the determination of optimized, transition structures, force constants, and intrinsic reaction pathways for the solute/solvent system, and to molecular dynamics calculations to account for finite temperature effects. As an illustration we characterize the structure and energy of micro-solvated formaldehyde H2CO in its ground state and in its 1(p*n) excited state. A novel perpendicular structure is found to be the lowest energy conformation of the H2CO1(p*n):H2O complex. The all-quantum chemical results and the mixed Hamiltonian results, with or without solvent polarizability, are in semi-quantitative agreement. We comment on the choice of Lennard-Jones parameters associated with a solute excited state. Lennard-Jones parameters that yield good ground state structuresmore » and energies with the mixed Hamiltonian model, are found to be too soft for the micro-solvated excited state H2CO in the adiabatic (equilibrium micro-solvation) regime.« less

Authors:
 [1];  [2];  [3];  [3]
  1. BATTELLE (PACIFIC NW LAB)
  2. Hiroshima University
  3. University of Tokyo
Publication Date:
Research Org.:
Pacific Northwest National Lab., Richland, WA (US) (US)
Sponsoring Org.:
US Department of Energy (US)
OSTI Identifier:
15001412
Report Number(s):
PNNL-SA-36411
KC0301020; TRN: US200324%%215
DOE Contract Number:  
AC06-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 117; Journal Issue: 3; Other Information: PBD: 15 Jul 2002
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTRONIC STRUCTURE; EXCITED STATES; FORMALDEHYDE; GROUND STATES; HAMILTONIANS; POLARIZATION; TEMPERATURE DEPENDENCE; SOLVATION; MOLECULAR DYNAMICS METHOD

Citation Formats

Dupuis, Michel, Aida, M A, Kawashima, Y, and Hirao, Kimihiko. Polarizable Mixed Hamiltonian Model of Electronic Structure for Micro-solvated Excited States. I. Energy and Gradients Formulation and Application to Formaldehyde (1A2).. United States: N. p., 2002. Web. doi:10.1063/1.1483858.
Dupuis, Michel, Aida, M A, Kawashima, Y, & Hirao, Kimihiko. Polarizable Mixed Hamiltonian Model of Electronic Structure for Micro-solvated Excited States. I. Energy and Gradients Formulation and Application to Formaldehyde (1A2).. United States. https://doi.org/10.1063/1.1483858
Dupuis, Michel, Aida, M A, Kawashima, Y, and Hirao, Kimihiko. 2002. "Polarizable Mixed Hamiltonian Model of Electronic Structure for Micro-solvated Excited States. I. Energy and Gradients Formulation and Application to Formaldehyde (1A2).". United States. https://doi.org/10.1063/1.1483858.
@article{osti_15001412,
title = {Polarizable Mixed Hamiltonian Model of Electronic Structure for Micro-solvated Excited States. I. Energy and Gradients Formulation and Application to Formaldehyde (1A2).},
author = {Dupuis, Michel and Aida, M A and Kawashima, Y and Hirao, Kimihiko},
abstractNote = {We describe an efficient implementation of a polarizable mixed Hamiltonian model of electronic structure that combines Hartree-Fock , Kohn-Sham, or multiconfiguration quantum chemical wavefunctions with a polarizable and flexible molecular mechanics potential of water, and that is applicable to micro-solvated electronic excited states. We adopt a direct algorithm for the calculation of the polarization response of the solvent subsystem. The strategy facilitates the calculation of the energy of the system and of the forces with respect to the solute coordinates and the solvent coordinates, including for excited states. This capability opens the way to the determination of optimized, transition structures, force constants, and intrinsic reaction pathways for the solute/solvent system, and to molecular dynamics calculations to account for finite temperature effects. As an illustration we characterize the structure and energy of micro-solvated formaldehyde H2CO in its ground state and in its 1(p*n) excited state. A novel perpendicular structure is found to be the lowest energy conformation of the H2CO1(p*n):H2O complex. The all-quantum chemical results and the mixed Hamiltonian results, with or without solvent polarizability, are in semi-quantitative agreement. We comment on the choice of Lennard-Jones parameters associated with a solute excited state. Lennard-Jones parameters that yield good ground state structures and energies with the mixed Hamiltonian model, are found to be too soft for the micro-solvated excited state H2CO in the adiabatic (equilibrium micro-solvation) regime.},
doi = {10.1063/1.1483858},
url = {https://www.osti.gov/biblio/15001412}, journal = {Journal of Chemical Physics},
number = 3,
volume = 117,
place = {United States},
year = {2002},
month = {7}
}