Journal of Chemical Physics
This paper presents the first ab initio attempt to reconstruct the observed band profile of the stretching fundamental vFX (X=H,D) in the FX⋅⋅⋅O(CH3)2 hydrogen‐bonded system. The two‐dimensional potential energy surface V(rFH,RF⋅⋅⋅O) is evaluated by means of large basis set SCF calculations. The related force constants up to the fourth order are obtained via the analytical fit to a polynomial expansion. The vibrational problem is solved by means of a variational treatment which includes the effects of mechanical anharmonicity. The side bands of the stretching fundamental vFX are described in terms of the vFX ±nvFX⋅⋅⋅O combination bands in excellent agreement with experiment.
Theoretical vibrational study of the FX [center-dot] [center-dot] [center-dot] O(CH[sub 3])[sub 2] hydrogen-bonded complex Y. Bouteiller, C. Mijoule, M. M. Szczesniak, and S. Scheiner, J. Chem. Phys. 88, 4861 (1988), DOI:10.1063/1.454697