Chemical hardness and the discontinuity of the Kohn-Sham exchange-correlation potential

Abstract

Chemical hardness, identified as the difference between the vertical first ionization potential I and the vertical electron affinity A, is analyzed in the context of the ionization theorems to derive expressions for its evaluation at different levels of approximation that arise as a direct consequence of the derivative discontinuity of the exchange-correlation potential. The quantities involved in these expressions incorporate indirectly the effects of the discontinuity, but their values may be calculated with any functional of the local density approximation, generalized gradient approximation, or optimized effective potential type, with or without derivative discontinuity, and with or without the correct asymptotic behavior. By comparison with the vertical energy difference values of I and A, which requires the calculation of the N-, (N-1)-, and (N+1)-electron systems, it is found, for a set of 14 closed shell molecules, that the difference between the eigenvalues of the highest occupied molecular orbitals of the N- and (N+1)-electron systems leads to rather accurate values, when the correct asymptotic behavior is incorporated, and that a second-order one-body perturbation approach that only requires information from the N-electron system leads to reasonable values.