On the synergy of matrix-isolation infrared spectroscopy and vibrational configuration interaction computations

The key feature of matrix-isolation infrared (MI-IR) spectroscopy is the isolation of single guest molecules in a host system at cryogenic conditions. The matrix mostly hinders rotation of the guest molecule, providing access to pure vibrational features. Vibrational self-consistent field (VSCF) and configuration interaction computations (VCI) on ab initio multimode potential energy surfaces (PES) give rise to anharmonic vibrational spectra. In a single-sourced combination of these experimental and computational approaches, we have established an iterative spectroscopic characterization procedure. The present article reviews the scope of this procedure by highlighting the strengths and limitations based on the examples of water, carbon dioxide, methane, methanol, and fluoroethane. An assessment of setups for the construction of the multimode PES on the example of methanol demonstrates that CCSD(T)-F12 level of theory is preferable to compute (a) accurate vibrational frequencies and (b) equilibrium or vibrationally averaged structural parameters. Our procedure has allowed us to uniquely assign unknown or disputed bands and enabled us to clarify problematic spectral regions that are crowded with combination bands and overtones. Besides spectroscopic assignment, the excellent agreement between theory and experiment paves the way to tackle questions of rather fundamental nature as to whether or not matrix effects are systematic, and it shows the limits of conventional notations used by spectroscopists. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s00214-020-02682-0) contains supplementary material, which is available to authorized users.