Asymptotic behavior of the average local ionization energy in finite basis sets.

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.