Analytic evaluation of Raman intensities in coupled-cluster theory

Abstract

We present the first implementation for the analytic calculation of polarizability derivatives using coupled-cluster theory. These derivatives are related to the intensity of bands seen in Raman spectroscopy, and are therefore important quantities that can also be measured experimentally. The required theory of analytic third derivatives is discussed and also connected to response theory to allow the calculation of frequency-dependent quantities. This work includes the use of a string-based general coupled-cluster/configuration-interaction program which makes the calculation of Raman intensities for arbitrary coupled-cluster or configuration-interaction methods up to the full configuration-interaction limit possible. Some demonstrative examples are given, with some investigation into the importance of higher-order excitations in the theoretical predictions of Raman intensities.