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Complete basis set extrapolated potential energy, dipole, and polarizability surfaces of alkali halide ion-neutral weakly avoided crossings with and without applied electric fields

Timothy J. Giese, Darrin M. York
J. Chem. Phys. (2004) 120, 7939
DOI: 10.1063/1.1690232
PMID: 15267709

Complete basis set extrapolations of alkali halide (LiF, LiCl, NaF, NaCl) energy, dipole, and polarizabilitysurfaces are performed with and without applied fields along the internuclear axis using state-averaged multireference configuration interaction. Comparison between properties (equilibrium separation, dissociation energy, crossing distance, diabatic coupling constant, dipole, and polarizability) derived from the extrapolated potential energy (or dipole) surfaces are made with those obtained from direct extrapolation from the basis set trends. The two extrapolation procedures are generally found to agree well for these systems. Crossing distances from this work are compared to those of previous work and values obtained from the Rittner potential. Complete basis set extrapolated crossing distances agree well with those derived from the Rittner potential for LiF, but were significantly larger for LiCl, NaF, and NaCl. The results presented here serve as an important set of benchmark data for the development of new-generation many-body force fields that are able to model charge transfer.

Research Areas: Quantum Biophysics

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