ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
We have used ab initio methods to characterize the Ne–HF van der Waals complex. The interaction energy was determined using size consistent, correlated CEPA wave functions expanded in a Gaussian basis chosen to represent both intraatomic effects and the low order multipole moments and polarizabilities of Ne and HF. The calculated well depths are −65 cm−1 for linear Ne–HF and −39 cm−1 for linear Ne–FH, with an intervening saddle point at −27 cm−1. The induction contribution to the energy is significantly greater for Ne–HF than for Ne–FH, but dispersion remains the dominant attraction over the region of interest. Converged variational and close-coupling calculations using the ab initio potential surface reveal three bound levels of the Ne–HF stretch mode, and several metastable levels correlating asymptotically with rotationally excited HF( j=1). Though nearly degenerate, the lifetimes of the two metastable Π (body frame Λ=±1) bending levels differ markedly because of different rotational coupling strengths to the Σ (body frame Λ=0) bending state, which undergoes rapid rotational predissociation. From the calculated line positions, widths, and intensities we have synthesized far infrared and infrared spectra of Ne–HF and Ne–DF.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.457177
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