Absolute intensities of Raman trace scattering from bicyclo-[1.1.1]-pentane

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Abstract
Our previous theoretical studies have identified the Raman intensity parameter for the bridgehead C–H stretch in bicyclo-[1.1.1]-pentane as the largest for any saturated hydrocarbon yet considered, while the methylene C–H parameter is predicted to be ordinary. Theoretical methods including self-consistent field, static and time dependent density functional theory, and coupled cluster, all predict a large bridgehead intensity parameter, but differ widely in the actual value. We have synthesized bicyclo-[1.1.1]-pentane and recorded the absolute intensity Raman trace scatteringspectra. The recorded intensity of a resonance polyad in the C–H stretching region has been resolved and distributed onto the fundamental modes through an anharmonic resonance analysis from a computed quartic force field. The experimental internal coordinate intensity parameters have been obtained and compared with those computed. Although the static and dynamic density functional values overestimate the parameter by 10%–18%, the values predicted at the coupled-cluster level are found to be correct to within experimental error.