Partial third‐order quasiparticle theory: Comparisons for closed‐shell ionization energies and an application to the Borazine photoelectron spectrum

1996 ◽  
Vol 104 (19) ◽  
pp. 7599-7605 ◽  
Author(s):  
J. V. Ortiz
Keyword(s):  
Photoelectron Spectrum ◽  
Closed Shell ◽  
Third Order ◽  
Ionization Energies ◽  
Shell Ionization

scholarly journals The high-energy band in the photoelectron spectrum of alkanes and its dependence on molecular structure

1999 ◽  
Vol 64 (11) ◽  
pp. 673-680 ◽  
Author(s):  
Ivan Gutman ◽  
Viktorija Gineityte ◽  
Mirko Lepovic ◽  
Miroslav Petrovic
Keyword(s):  
Molecular Structure ◽  
Energy Band ◽  
Photoelectron Spectrum ◽  
Line Graph ◽  
Energy Levels ◽  
Molecular Graph ◽  
High Energy ◽  
Saturated Hydrocarbons ◽  
Ionization Energies ◽  
Laplacian Eigenvalues

In the model for the ionization energies of the C2s-electrons in saturated hydrocarbons, put forward by Heilbronner et al., the energy levels are calculated as eigenvalues of the line graph of the hydrogen-filled molecular graph. It is now shown that in the case of alkanes, these energy levels are related to the Laplacian eigenvalues of the molecular graph. A few rules are formulated, relating these ionization energies with molecular structure.

∆SCF and Transition Operator (TO) Calculations in the Theoretical Determination of Vertical Ionization Energies in Transition Metal Compounds

1981 ◽  
Vol 36 (11) ◽  
pp. 1205-1212 ◽  
Author(s):  
Michael C. Böhm
Keyword(s):  
Transition Metal ◽  
Transition Metal Compounds ◽  
Transition Operator ◽  
Electron Interaction ◽  
Third Order ◽  
Metal Compounds ◽  
Ionization Energies ◽  
Valence Region ◽  
Vertical Ionization Potentials ◽  
The Difference

The interrelation between theoretically determined vertical ionization potentials in transition metal compounds based on the ∆SCF approximation (Iv,j∆SCF) and based on the “transition operator (TO)” method (Iv,jTO) has been investigated. Numerical results in the outer valence region have been obtained by means of semiempirical INDO calculations. The difference between the calculated ionization energies (Iv,j∆SCF and Iv,jTO) is enlarged with increasing atomic numbers of the transition metal center due to noncompensating terms in third order of perturbation. The neces­sary conditions for the imbalance of both theoretical procedures are large two-electron interaction integrals and highly populated transition metal hole-states. Both requirements are enhanced by going from the left side of the 3d series to the extreme right. For d4-d6 complexes a simplified expression for Iv,j∆SCF has been derived containing only one third order element.

Effects of molecular conformation on inner-shell ionization energies

2007 ◽  
Vol 9 (6) ◽  
pp. 719-724 ◽  
Author(s):  
T. D. Thomas ◽  
L. J. Sæthre ◽  
K. J. Børve
Keyword(s):  
Molecular Conformation ◽  
Ionization Energies ◽  
Inner Shell Ionization ◽  
Shell Ionization

THE ESTIMATIONS OF INNER-SHELL IONIZATION ENERGIES FOR ALKYL HALIDES: A DESIGNATED SINGLE-CONFIGURATION CASSCF APPROACH AND ADVANCED CORRECTION

2004 ◽  
Vol 03 (01) ◽  
pp. 103-115
Author(s):  
CHIN-HUI YU ◽  
JEN-SHIANG K. YU ◽  
WEI-CHEN CHEN
Keyword(s):  
Alkyl Halides ◽  
Basis Sets ◽  
Ionization Energies ◽  
Consistent Field ◽  
Valence Electrons ◽  
Self Consistent Field ◽  
Franck Condon ◽  
Vertical Ionization Energies ◽  
Shell Ionization ◽  
Single Configuration

Based on the Franck–Condon principle, vertical ionization energies regarding the inner-shell valence electrons of alkyl halides and their unsaturated analogues were evaluated with a designated single-configuration complete active self-consistent field (CASSCF) approach as well as the advanced correction with configuration interaction. Excitations corresponding to the elimination of one electron from a specific molecular orbital of these species were calculated by the deviation between the energy of the SCF-optimized neutral structure and of its cation. The freezing over the outer orbitals with identical symmetry was achieved while performing the CASSCF ionization calculation for the inner orbitals. These energy evaluations utilized Pople's 6-31G*, 6-311G** and Roos' ANO basis sets. Computed results agreed well with the experimental data. The characters for the molecular orbitals of corresponding vertical ionizations could be qualitatively assigned by the MOLDEN visualization program.

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