Localized Orbital Scaling Correction to Linear-Response Time-Dependent Density Functional Approximations

The localized orbital scaling correction (LOSC) method, which was developed for eliminating the delocalization error in density functional approximations (DFAs), is extended to the linear-response regime for calculating excitation energies with time-dependent density functional theory (TDDFT). Corrections to the exchange-correlation kernel are derived within the frozen-orbitalet approximation. Extensive numerical tests on various data sets show that LOSC-DFAs are able to maintain the good performance of parent DFAs for valence excitations while systematically improving the excitation energies for Rydberg and charge-transfer excitations by reducing the delocalization error. For charge-transfer excitations, LOSC can produce correct asymptotic behaviors with the donor–acceptor separation R as well as the excitation energy at the infinite separation limit. Moreover, through the example of trans-polyacetylene oligomers, we demonstrate that the performance of LOSC does not deteriorate with increasing system size, holding promise for application in bulk systems.