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Pseudosymmetry analysis of molecular orbitals
Author(s) -
Casanova David,
Alemany Pere,
Falceto Andrés,
Carreras Abel,
Alvarez Santiago
Publication year - 2013
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.23257
Subject(s) - localized molecular orbitals , molecular orbital , natural bond orbital , atomic orbital , linear combination of atomic orbitals , computer science , computational chemistry , chemistry , physics , molecule , quantum mechanics , density functional theory , electron
We introduce a pseudosymmetry analysis of molecular orbitals by means of the newly proposed irreducible representation measures. To do that we define first what we consider as molecular pseudosymmetry and the relationships of this concept with those of approximate symmetry and quasisymmetry. We develop a general algorithm to quantify the pseudosymmetry content of a given object within the framework of the finite group algebra. The obtained mathematical expressions are able to decompose molecular orbitals by means of the irreducible representations of any reference symmetry point group. The implementation and usefulness of the pseudosymmetry analysis of molecular orbitals is demonstrated in the study of σ and π orbitals in planar and nonplanar polycyclic aromatic hydrocarbons and the t 2 g and e g character of the d‐orbitals in the [FeH 6 ] 3− anion in its high spin state along the Bailar twist pathway. © 2013 Wiley Periodicals, Inc.