Local vibrational force constants – From the assessment of empirical force constants to the description of bonding in large systems

Abstract

The local vibrational mode analysis, originally introduced by Konkoli and Cremer, provides a physically sound platform for a comprehensive analysis of calculated or measured vibrational spectra and for providing detailed insights into chemical bonding and other structural features. In this work, we summarize the essentials of the local vibrational mode theory with a focus on local vibrational force constants and their relationship with compliance and relaxed force constants. Furthermore, we discuss how local vibrational force constants can be used (i) to assess the quality of empirically derived force constants, (ii) to disclose bonding features in large molecules, and (iii) to provide metal ligand force field parameters. Future applications will be suggested.