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Electron affinities, gas phase acidities, and potential energy curves: Benzene
Author(s) -
Jalbout A. F.,
Trzaskowski B.,
Chen E. C. M.,
Chen E. S.,
Adamowicz Ludwik
Publication year - 2006
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.21237
Subject(s) - chemistry , electron affinity (data page) , excited state , singlet state , ion , benzene , ionic bonding , atomic orbital , ab initio , computational chemistry , density functional theory , affinities , electron , atomic physics , stereochemistry , molecule , physics , quantum mechanics , organic chemistry
The experimental electron affinities of benzene, E a (Bz), 0.4 to −4.8 eV, are evaluated. Multiple negative ion states are proposed to account for different electron affinities. The semi‐empirical procedure known as “configuration interaction or unrestricted orbitals to relate experimental quantities to self‐consistent field values by estimating electron correlation” (CURES‐EC) has several advantages: (i) supports multiple E a (Bz), (ii) supports the E a (phenyl) and the D(CH,Bz), (iii) supports the gas phase acidity of benzene from the latter, (iv) predicts the singlet–triplet split for the phenyl anion of 1.2(2) eV, and (v) predicts the existence of an excited quartet state of the benzene anion with an E a (Bz), −2.5(2) eV. Nine ionic Morse curves are calculated from CURES‐EC properties and experimental data. These are compared with quantum mechanical crossing “c” potentials obtained using a subroutine in commercial software and ab initio and density functional theory (DFT) procedures. Curves are calculated for the proposed quartet state of the benzene anion. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007