ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The concept of atomic orbital basis sets that float with the nuclear positions is extended to include floating with the nuclear velocities. With such basis functions the contribution to vibrational dipole and rotational strengths from electronic motion that perfectly follows the nuclear motion can be calculated from the equilibrium ground state electronic wave function. Contributions from electronic current due to charge redistribution are determined from vibronic summations that require nuclear displacement derivatives of ground state linear combination of atomic orbitals (LCAO) coefficients. In addition, for the dipole velocity and magnetic dipole operators, a contribution from charge flow at constant electron density enters. The relationships between this formulation, other vibronic coupling models, and approximate ground state models for vibrational circular dichroism intensities are described.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.455479
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