Spin-state splittings, highest-occupied-molecular-orbital and lowest-unoccupied-molecular-orbital energies, and chemical hardness.

Published

Journal Article

It is known that the exact density functional must give ground-state energies that are piecewise linear as a function of electron number. In this work we prove that this is also true for the lowest-energy excited states of different spin or spatial symmetry. This has three important consequences for chemical applications: the ground state of a molecule must correspond to the state with the maximum highest-occupied-molecular-orbital energy, minimum lowest-unoccupied-molecular-orbital energy, and maximum chemical hardness. The beryllium, carbon, and vanadium atoms, as well as the CH(2) and C(3)H(3) molecules are considered as illustrative examples. Our result also directly and rigorously connects the ionization potential and electron affinity to the stability of spin states.

Full Text

Duke Authors

Cited Authors

  • Johnson, ER; Yang, W; Davidson, ER

Published Date

  • October 2010

Published In

Volume / Issue

  • 133 / 16

Start / End Page

  • 164107 -

PubMed ID

  • 21033775

Pubmed Central ID

  • 21033775

Electronic International Standard Serial Number (EISSN)

  • 1089-7690

International Standard Serial Number (ISSN)

  • 0021-9606

Digital Object Identifier (DOI)

  • 10.1063/1.3497190

Language

  • eng