Abstract
AbstractMost of the anharmonic constants of trichlorosilane and ‐methane have been determined, with special emphasis to the values of x1i, i = 1 to 6. In both molecules, there is a strong Fermi resonance between hydrogen stretch and bend vibrations and Coriolis interaction between ν2 and ν5. Some irregularities in the hot band structures point to an interaction of ν1 with ν2 + 2ν4 and other higher order interactions. In SiHCl3, x13 and x16 are near 0, in agreement with a rule that nondiagonal anharmonicities between high‐ and low‐frequency vibrations tend to be small. In CHCl3, the corresponding values are larger, though still small. We discuss a possible correlation of such values with the frequency change of one of the vibrations, if the bond corresponding to the other one is dissociated. Ni(CO)4 is quoted as a further example. The data set could help in calculations of vibrational relaxation rates.
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