A Validation of Cluster Modeling in the Description of Matrix Isolation Spectroscopy.

Matrix isolation is a fundamental tool for the synthesis and characterization of highly reactive novel species and investigation of unusual bonding situations. Ab initio descriptions of guest-host interactions in matrix isolation are highly demanding, as the weak interactions between guest and host can influence the former's oftentimes challenging electronic structure. In this study, the matrix effects on a single CO molecule in an argon matrix were investigated with dispersion-corrected density functional theory calculations. Three different guest-host structures were described by bulk models employing periodic boundary conditions as well as cluster models. The calculations were analyzed with respect to structural features of the CO molecule and its immediate surroundings. Also, the molecule's harmonic frequencies were determined. The calculated frequencies were in qualitative agreement with experimental observations. The cluster models produced comparable results given that the clusters were large enough to reproduce the structural features of the bulk model. © 2019 Wiley Periodicals, Inc.