Anharmonic Spectroscopic Investigation of Tellurophene and Its Perdeuterated Isotopomer: Application of Second-Order Perturbation Theory

Abstract

Vibrational spectra of tellurophene and of its perdeuterated isotopomer were computed using the DFT-B3LYP functional with the LANL2DZ(d,p) basis set. The frequencies of fundamental and overtone transitions were obtained in vacuum under the harmonic approximation and anharmonic second-order perturbation theory (PT2). On the whole the anharmonic corrections reduce the harmonic wavenumber values, in many cases better reproducing the observed fundamental frequencies. The largest anharmonic effects are found for the C–H and C–D stretching vibrations, characterized by relatively high anharmonic coupling constants (up to ca. 120 cm −1 ). For the C–H/C–D stretches, the harmonic H→D isotopic frequency red-shifts overestimate the observed data by 47–63 cm −1 (5.9–8.1%), whereas the PT2 computations exhibit significantly better performances, predicting the experimental data within 1–19 cm −1 (0.1–2.4%).