Single and Double Core-Hole Ionization Energies in Molecules

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• 作者：T. Darrah Thomas
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：April 19, 2012
• 年：2012
• 卷：116
• 期：15
• 页码：3856-3865
• 全文大小：387K
• 年卷期：v.116,no.15(April 19, 2012)
• ISSN：1520-5215

文摘

The recently demonstrated ability to measure double-hole core-ionization energies in first-row elements has led to a renewed interest in the use of such energies to investigate the effects of initial-state charge distribution and final-state charge rearrangement on the energies of chemical processes that involve addition of charge to a molecule. With theoretical calculations for the molecules CH_4鈥?i>nX_n, X = F, Cl, and for C(CH₃)₄ as a basis, the relationships between one-hole and two-hole ionization energies, on one hand, and initial-state and final-state effects, on the other, are reviewed. It is shown that higher-order corrections to the traditionally used relationships are quantitatively significant but do not lead to qualitatively different conclusions. The role of the Wagner plot as a way to display the relationships among the various quantities of interest is discussed, and a generalized Wagner plot for displaying two-site double-hole ionization energies is presented. Some possible applications of measurements of double-hole ionization energies to the investigation of molecular conformation and molecular fragmentation are discussed.