Document Type

Article

Publication Date

1987

Publication Title

The Journal of Chemical Physics

First Page

4478

Last Page

4486

DOI

http://dx.doi.org/10.1063/1.452861

Abstract

Observation of the 2ν1 overtone band in the hydrogen‐bonded complex HCN‐‐‐HF permits evaluation of the anharmonicity constant X 1 1=−116.9(1) cm− 1 and determination of the anharmonicity corrected fundamental frequency ω1. This information, and available data from previous rovibrational analyses in the common and perdeuterated isotopic species of HCN‐‐‐HF, offer an opportunity for calculation of an approximate stretching harmonic force field. With the assumptions f 1 2=f 2 4=0.0, the remaining force constants (in mdyn/Å) are evaluated as: f 1 1=8.600(20), f 2 2=6.228(9), f 3 3=19.115(40), f 4 4=0.2413(39), f 1 3=0.000(13), f 1 4=0.0343(2), f 2 3=−0.211(6), f 3 4=0.000(2). These compare to f 1 1=9.658(2) in the HF monomer and f 1 1=6.244(3) and f 3 3=18.707(16) in the HCN monomer. These results provide the information necessary to quantitatively assess the applicability of the Cummings and Wood approximation in this hydrogen‐bonded complex and also give an estimate of D e j , the equilibrium distortion constant in the harmonic limit. Comparisons of these experimentally determined parameters with the predictions of a b i n i t i o molecular orbital calculations at several levels of approximation are presented.

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This article was archived with permission from AIP Publishing, all rights reserved. Document also available from The Journal of Chemical Physics.

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