Ab initio calculations of stretching vibrational transitions for the linear molecules HCN, HNC, HCCF and HC3N up to high overtones Original Research Article

Accurate electric dipole moment functions have been calculated for the stretching vibrational coordinates of the linear molecules HCN, HNC, HCCF and HC3N by means of coupled cluster theory with single and double excitation operators plus a quasi-perturbative treatment of connected triples (CCSD(T)). Combining these with anharmonic stretching vibrational wave-functions absolute IR intensities for strecthing vibrational transitions up to high overtones are obtained. For HCN, excellent agreement with experiment is observed up to 7 ν1 + η3 at 23047 cm−1. HCCF and DCCF show unusual behavior, with the ν2 band with origin at 2239.2 cm−1 being strongest in HCCF and the ν1 band with origin at 2645.1 cm−1 being the most intense in DCCF. The Fermi resonance system 2ν3/ν2 of DCCF is analysed in detail. The calculated IR intensities of the stretching fundamentals of HC3N and DC3N, which are difficult to obtain with high accuracy, are in very good agreement with the existing experimental data.