ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The magnitude of reorganization energies in the photoelectron (PE) spectra of various transition metal compounds with Mn, Fe, and Ni as 3d center is studied by means of a variable INDO Hamiltonian. The Koopmans defects are analyzed as a function of the one-electron resonance integral βμνAB and as function of the one- and two-center electron-electron interaction integrals. βμνAB has the property of an inverse coupling constant; reorganization effects are enlarged with reduced βμνAB values. In the limit of very small resonance integrals a reduction of the calculated Koopmans defects due to modified localization properties of the orbital wave function is encountered. The two-center electron-electron interaction integrals γμνAB have been calculated via an exponential formula with a variable range parameter. In the limit of long-range potentials with flattened γ;μνAB gradients a significant reduction of relaxation and correlation is diagnozed; large defects are predicted in the short-range limit with steep gradients in the repulsion potential. The one-center Coulomb and exchange integrals (γμνAA, KμνAA) have been modified by a multiplicative factor. With enlarged one-center integrals enhanced Koopmans defects are encountered. The reorganization energies are determined by means of a Green's function approach with a renormalized approximation for the self-energy part.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560220508
