A Simple Range-Separated Double-Hybrid Density Functional Theory for Excited States.

ABSTRACT: A simple and robust range-separated (RS) double-hybrid (DH) time-dependent density functional approach is presented for the accurate calculation of excitation energies of molecules within the Tamm-Dancoff approximation. The scheme can be considered as an excited-state extension of the ansatz proposed by Toulouse and co-workers [J. Chem. Phys. 2018, 148, 164105], which is based on the two-parameter decomposition of the Coulomb potential, for which both the exchange and correlation contributions are range-separated. A flexible and efficient implementation of the new scheme is also presented, which facilitates its extension to any combination of exchange and correlation functionals. The performance of the new approximation is tested for singlet excitations on several benchmark compilations and thoroughly compared to that of representative DH, RS hybrid, and RS DH functionals. The one-electron basis set dependence and computation times are also assessed. Our results show that the new approach improves on standard DHs in most cases, and it can provide a more robust and accurate alternative. In addition, on average, it noticeably surpasses the existing RS hybrid and RS DH functionals.

SUBMITTER: Mester D 

PROVIDER: S-EPMC7884002 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature