ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Nonadiabatic matrix elements, when computed using a Born-Oppenheimer (BO) basis, do not vanish asymptotically because the motion of the electrons with the nuclei at large internuclear separations is not taken into account. We apply a method suggested by Delos [Rev. Mod. Phys. 53, 287 (1981)] to include the effect of electron translation factors in a quantum-mechanical framework, thus correcting the BO basis to incorporate proper boundary conditions. We calculate the nonadiabatic matrix elements for H2+ and its isotopic variants. We focus our calculations on HD+, for which experimental results exist, and calculate its vibronic spectrum. This is the first application of this method to calculate high precision spectroscopic information for molecular systems. © 1999 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.479877
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