While the inclusion of relativistic effects in studies of energetics and electronic states of molecules containing heavier elements is prevalent throughout the literature, the inclusion of these effects for higher-order response properties has hardly been investigated. A new methodology for calculating such higher-order responses including relativistic effects has been developed in the Ruud group. Here we have applied this methodology to investigate the effects of  relativity on the the polarizability, and the 1st and 2nd hyperpolarizabilities respectively, of the furan, thiophene, selenophene, and tellurophene series with and without the inclusion of pure vibrational effects.  We find that with increasing size of the heteroatom, the relativistic effects increase with the scalar relativistic effects dramatically outpacing the spin-orbital coupling effects. Additionally the 2nd and 3rd order properties are considerably more sensitive to these effects than the 1st order response. We also investigated the pure vibrational corrections and found that the vibrational corrections were much more sensitive to the effects of relativity than the electronic component of the hyperpolarizability.

Identifying relativistic effects on (hyper)polarizabilities

244th National Meeting (2012)

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