Article
Electron Affinity of 0- and Diabatic CaO(g) Integer Charge Potential Curves
Journal of the American Chemical Society
(1990)
Abstract
A ligand field, integer-charge ionic model for the electronic structure of diatomic CaO(g) provides a basis for an
empirical deperturbation of the lowest lying '2' electronic states to their diabatic doubly charged (Ca2+02-)a nd singly charged ionic (Ca'O-) potentials. The deperturbed doubly charged and lowest singly charged potentials cross at rCa-O = 2. I6 ( I ) 8, at an cncrgy 10400 (100) cm-I above u = 0 of the experimentally observed X'Z+ ground state. The interaction matrix elements bctwccn thc thrcc lowcst intcracting IZ+ states have been determined as functions of rca+ With use of a simple Rittner model for thc diabatic curves, cxtrapolation to infinite internuclear separation yields a value for the electron affinity of 0- (i.e., 0- + c- - 02-o)f -4.53 (6) eV, in agreement with quantum-chemical results, and a value of 35 160 (200) cm-1 forD0 0 of CaO, in excellent agreement with thermochemical values.
Disciplines
Publication Date
December, 1990
DOI
10.1021/ja00181a019
Publisher Statement
Reprinted (adapted) with permission from Journal of the American Chemical Society 112 (1990): 9156, doi: 10.1021/ja00181a019. Copyright 1990 American Chemical Society.
Citation Information
David P. Baldwin, Ernest J. Hill and Robert W. Field. "Electron Affinity of 0- and Diabatic CaO(g) Integer Charge Potential Curves" Journal of the American Chemical Society Vol. 112 Iss. 25 (1990) p. 9156 - 9161 Available at: http://works.bepress.com/david-baldwin/4/