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Calculation of thermochemical properties of conjugated radicals
Author(s) -
Vysotsky Y. B.,
Bryantsev V. S.
Publication year - 2003
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.10545
Subject(s) - radical , chemistry , open shell , conjugated system , computational chemistry , hamiltonian (control theory) , perturbation theory (quantum mechanics) , basis set , standard enthalpy of formation , molecule , quantum chemical , quantum , density functional theory , organic chemistry , quantum mechanics , physics , polymer , mathematics , mathematical optimization
Abstract Heat of formation for 30 conjugated hydrocarbon radicals were calculated within the framework of an unrestricted Hartree–Fock method using the same set of π‐Hamiltonian parameters for systems with closed and open electronic shell. Based on π‐electronic perturbation theory, the model of aromatic annelation and radical CH 2 substitution of neutral molecules was developed. The proposed model makes it possible to obtain thermochemical properties of radicals on the basis of calculated or experimental data for less lengthy analogues. Direct calculation and results based on perturbation theory agree closely with each other and with experiment. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004