%0 Journal Article %1 Oneil1989 %A Oneil, S. V. %A Nesbitt, D. J. %A Rosmus, P. %A Werner, H. J. %A Clary, D. C. %D 1989 %J J. Chem. Phys. %K chemie imported werner from:alexanderdenzel theoretische stuttgart theochem %N 2 %P 711–721 %R 10.1063/1.457177 %T Weakly bound NeHF %U http://dx.doi.org/10.1063/1.457177 %V 91 %X 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. © 1989 American Institute of Physics.

@article{Oneil1989, abstract = {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. {\textcopyright} 1989 American Institute of Physics.}, added-at = {2019-03-01T15:49:40.000+0100}, author = {Oneil, S. V. and Nesbitt, D. J. and Rosmus, P. and Werner, H. J. and Clary, D. C.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/298311515edc3631f08985c8e88460b8a/theochem}, doi = {10.1063/1.457177}, interhash = {fdfce15346803b64035e4167e1017dec}, intrahash = {98311515edc3631f08985c8e88460b8a}, issn = {00219606}, journal = {J. Chem. Phys.}, keywords = {chemie imported werner from:alexanderdenzel theoretische stuttgart theochem}, month = jul, number = 2, pages = {711–721}, timestamp = {2019-03-01T14:49:40.000+0100}, title = {{Weakly bound NeHF}}, url = {http://dx.doi.org/10.1063/1.457177}, volume = 91, year = 1989 }