The interplay of VSCF/VCI calculations and matrix-isolation IR spectroscopy - Mid infrared spectrum of CH3CH2F and CD3CD2F

摘要

We present the first matrix-isolation infrared (MI-IR) spectra of CH3CH2F and its isotopologue CD3CD2F in Neon and Argon matrix, together with new gas-phase IR spectra. Extensive vibrational self-consistent field and configuration interaction (VSCF/VCI) calculations are performed, based on an ab initio potential energy surface at ae-CCSD(T)-F12a/cc-pCVTZ-F12 level of electronic structure theory. We encounter an excellent agreement between VCI calculated transitions and the experimental MI-IR and gas-phase IR spectra. Mean absolute deviations are scattering between 1 and 4 cm(-1). The interplay of accurate vibrational structure calculations and high-resolution infrared experiments enables unprecedented insights in the CH respectively CD stretch region, providing the first rigorous assignment of the energetically very close nu(1), nu(12) and nu(13) fundamental transitions. (C) 2019 The Authors. Published by Elsevier Inc.