The use of ab initio anharmonic force fields in experimental studies of equilibrium molecular geometry

Abstract

The use of ab initio methods has been investigated for obtaining physically meaningful anharmonic force fields applicable in structure analysis of molecules by electron diffraction. The quadratic and cubic force constants for the sample molecule SF6 chosen as a suitable test case were theoretically estimated and improved by an empirical scaling based on a quadratic force constant scale factors. It was confirmed that if theoretical calculations are made with well selected basis sets the accuracy of the individual values of the computed cubic constants established by reference to precise spectroscopic data is practically sufficient to experimentally determine the accurate equilibrium S–F distance and to theoretically estimate the amplitudes of vibration and the phase shift parameters for all internuclear distances. Calculations based on a Morse-like anharmonic model function were also performed for comparison.The present calculations show that determination of an accurate equilibrium molecular structure by electron diffraction is possible through the appropriate combination of experimental and theoretical data. The best equilibrium geometry results, if empirically scaled ab initio quadratic and cubic force constants are used in a regularizing algorithm developed earlier for the effective interaction of electron diffraction with vibrational and microwave spectroscopy techniques.