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Diabatic Population Matrix Formalism for Performing Molecular Mechanics Style Simulations with Multiple Electronic States
journal contribution
posted on 2014-12-09, 00:00 authored by Jae Woo Park, Young Min RheeAn accurate description of nonbonded
interactions is important
in investigating dynamics of molecular systems. In many situations,
fixed point charge models are successfully applied to explaining various
chemical phenomena. However, these models with conventional formulations
will not be appropriate in elucidating the detailed dynamics during
nonadiabatic events. This is mainly because the chemical properties
of any molecule, especially its electronic populations, significantly
change with respect to molecular distortions in the vicinity of the
surface crossing. To overcome this issue in molecular simulations
yet within the framework of the fixed point charge model, we define
a diabatic electronic population matrix and substitute it for the
conventional adiabatic partial charges. We show that this matrix can
be readily utilized toward attaining more reliable descriptions of
Coulombic interactions, in combination with the interpolation formalism
for obtaining the intramolecular interaction potential. We demonstrate
how the mixed formalism with the diabatic charges and the interpolation
can be applied to molecular simulations by conducting adiabatic and
nonadiabatic molecular dynamics trajectory calculations of the green
fluorescent protein chromophore anion in aqueous environment.
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Keywords
protein chromophore anionpoint charge modelpoint charge modelsnonadiabatic eventschemical propertiespopulation matrixinterpolation formalismDiabatic Population Matrix Formalismnonbonded interactionsdynamics trajectory calculationsdiabatic chargesintramolecular interactionCoulombic interactionsMolecular Mechanics Style Simulationssimulationchemical phenomenaMultiple Electronic StatesAn