Decoding chemical information from vibrational spectroscopy data: Local vibrational mode theory

Abstract

AbstractModern vibrational spectroscopy is more than just an analytical tool. Information about the electronic structure of a molecule, the strength of its bonds, and its conformational flexibility is encoded in the normal vibrational modes. On the other hand, normal vibrational modes are generally delocalized, which hinders the direct access to this information, attainable only via local vibration modes and associated local properties. Konkoli and Cremer provided an ingenious solution to this problem by deriving local vibrational modes from the fundamental normal modes, obtained in the harmonic approximation of the potential, via mass‐decoupled Euler–Lagrange equations. This review gives a general introduction into the local vibrational mode theory of Konkoli and Cremer, elucidating how this theory unifies earlier attempts to obtain easy to interpret chemical information from vibrational spectroscopy: (a) the local mode theory furnishes bond strength descriptors derived from force constant matrices with a physical basis, (b) provides the highly sought after extension of the Badger rule to polyatomic molecules, (c) and offers a simpler way to derive localized vibrations compared to the complex route via overtone spectroscopy. Successful applications are presented, including a new measure of bond strength, a new detailed analysis of infrared/Raman spectra, and the recent extension to periodic systems, opening a new avenue for the characterization of bonding in crystals. At the end of this review the LMODEA software is introduced, which performs the local mode analysis (with minimal computational costs) after a harmonic vibrational frequency calculation optionally using measured frequencies as additional input.This article is categorized under: Structure and Mechanism > Molecular Structures Theoretical and Physical Chemistry > Spectroscopy Software > Quantum Chemistry Electronic Structure Theory > Ab Initio Electronic Structure Methods