TITLE

Asymmetric adiabatic correction to the rotation–vibration levels of H2D+ and D2H+

AUTHOR(S)
Polyansky, Oleg L.; Dinelli, Bianca M.; Le Sueur, C. Ruth; Tennyson, Jonathan
PUB. DATE
June 1995
SOURCE
Journal of Chemical Physics;6/15/1995, Vol. 102 Issue 23, p9322
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Calculations on H2D+ and D2H+ have shown that the energy levels of these asymmetric isotopomers of H3+ cannot be reproduced using effective potential energy surfaces with D3h symmetry. It is shown that for these ions the adiabatic correction to the Born–Oppenheimer approximation has an asymmetric component which can be expressed as a mass-independent surface multiplied by a mass factor. An expression for this function is obtained from ab initio calculations. Use of this adiabatic correction is found to resolve the discrepancy with the levels of H2D+ and D2H+. The ab initio calculations reported reproduce the observed H2D+ transitions with an average error (obs-calc) of -8 MHz for the rotational transitions, -0.06 cm-1 for the ν1 band, -0.13 cm-1 for ν2, and -0.19 cm-1 for ν3. These errors are nearly constant for all transitions within a vibrational band. This gives a very accurate ab initio framework for predicting unobserved transition frequencies. © 1995 American Institute of Physics.
ACCESSION #
7641918

 

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