Chemistry Publications
Document Type
Article
Publication Date
2020
Journal
The Journal of Chemical Physics
Volume
153
Issue
13
URL with Digital Object Identifier
https://doi.org/10.1063/5.0023459
Abstract
The average local ionization energy (ALIE) has important applications in several areas of electronic structure theory. Theoretically, the ALIE should asymptotically approach the first vertical ionization energy (IE) of the system, as implied by the rate of exponential decay of the electron density; for one-determinantal wavefunctions, this IE is the negative of the highest-occupied orbital energy. In practice, finite-basis-set representations of the ALIE exhibit seemingly irregular and sometimes dramatic deviations from the expected asymptotic behavior. We analyze the long-range behavior of the ALIE in finite basis sets and explain the puzzling observations. The findings have implications for practical calculations of the ALIE, the construction of Kohn–Sham potentials from wavefunctions and electron densities, and basis-set development.
Notes
This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in [Asymptotic behavior of the average local ionization energy in finite basis sets. The Journal of Chemical Physics 153, 13 (2020)] and may be found at https://doi.org/10.1063/5.0023459.