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Correlating the vibrational spectra of structurally related molecules: A spectroscopic measure of similarity
Author(s) -
Tao Yunwen,
Zou Wenli,
Cremer Dieter,
Kraka Elfi
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25109
Subject(s) - measure (data warehouse) , molecular vibration , path (computing) , eigenvalues and eigenvectors , molecule , normal mode , similarity (geometry) , hot band , correlation , spectral line , vibrational partition function , chemistry , molecular physics , physics , mathematics , quantum mechanics , vibration , geometry , computer science , data mining , artificial intelligence , image (mathematics) , programming language
Using catastrophe theory and the concept of a mutation path, an algorithm is developed that leads to the direct correlation of the normal vibrational modes of two structurally related molecules. The mutation path is defined by weighted incremental changes in mass and geometry of the molecules in question, which are successively applied to mutate a molecule into a structurally related molecule and thus continuously converting their normal vibrational spectra from one into the other. Correlation diagrams are generated that accurately relate the normal vibrational modes to each other by utilizing mode‐mode overlap criteria and resolving allowed and avoided crossings of vibrational eigenstates. The limitations of normal mode correlation, however, foster the correlation of local vibrational modes, which offer a novel vibrational measure of similarity. It will be shown how this will open new avenues for chemical studies. © 2017 Wiley Periodicals, Inc.