Core-excitation energy calculations with a long-range corrected hybrid exchange-correlation functional including a short-range Gaussian attenuation (LCgau-BOP)

Abstract

We report the calculations of core-excitation energies of first-row atoms using the time-dependent density functional theory (DFT) and the long-range correction (LC) scheme for exchange-correlation functionals, including LC-BOP, Coulomb-attenuated method BLYP, and our recently developed LCgau-BOP method, which includes a flexible portion of short-range Hartree-Fock (HF) exchange through the inclusion of a Gaussian function in the LC scheme. We show that the LC scheme completely fails to improve the poor accuracy of conventional generalized gradient approximation functionals, while the LCgau scheme gives an accuracy which is an order of magnitude better than BLYP and significantly better than B3LYP. A reoptimization of the two parameters controlling the inclusion of short-range HF exchange in the LCgau method enables the errors to be reduced to the order of 0.1 eV which is competitive with the best DFT methods we are aware of. This reparametrization does not affect the LC scheme and therefore maintains the high accuracy of predicted reaction barrier heights. Moreover, while there is some loss in accuracy in thermochemical predictions compared to the previously optimized LCgau-BOP, rms errors in the atomization energies over the G2 test set are found to be comparable to B3LYP. Finally, we attempt to rationalize the success of the LC and LCgau schemes in terms of the well-known self-interaction error (SIE) of conventional functionals. To estimate the role of the SIE, we examine the total energy calculations for systems with a fractional number of electrons, not only in the highest occupied molecular orbital but also in the 1s-characterized core orbital. Our conclusion is that the inclusion of short-range HF exchange in LC-type functionals can significantly alleviate the problems of the SIE in the core region. In particular, we confirm that the absence of the SIE diagnostics in the core orbital energies correlates with the accurate prediction of core-excitation energies using the newly optimized LCgau approach.