Charge-Transfer Excitation Energies Expressed as Orbital Energies of Kohn-Sham Density Functional Theory with Long-Range Corrected Functionals.

ABSTRACT

Previously proposed theoretical schemes for estimating one-electron excitation energies using Kohn-Sham (KS) solutions with long-range corrected (LC) functionals are applied to the charge-transfer (CT) excitations of the ethylene···tetrafluoroethylene (C2H4-C2F4) system, and the CT complex between an aromatic donor (Ar = benzene, toluene, o-xylene, naphthalene, anthracene, and various meso-substituted anthracenes) and the tetracyanoethylene (TCNE) acceptor. The CT excited state is described well as a single-electron excitation between specific orbitals of donor and acceptor. Thus, CT excitation energies are well approximated by the orbital energies because of the satisfaction of the Koopmans-type theorem and the asymptotic behavior of the LC functional. We have examined three computational schemes scheme 1 employs the orbital energies for the neutral and cationic systems, scheme 2 utilizes orbital energies of just the cation, and in scheme 3, because the electron affinity of a molecule is the ionization energy of its anion, a scale factor is applied to enforce this identity. The present schemes reproduce the correct asymptotic behavior of CT excitation energy of C2H4···C2F4 for the long intermolecular distances and give good agreement with accurate ab initio results. Calculated CT excitation energies for Ar-TCNE are compared with those of TD-DFT and ΔSCF methods. Scheme 1 with the optimal range-separation parameter µ accurately reproduces CT excitation energies for all Ar-TCNE systems and gives good agreement with the best TD-DFT calculations and experiment. Scheme 1, scheme 3, and TD-DFT show similar tendencies with respect to the variation in µ. Scheme 2 and ΔSCF approaches are rather insensitive to changes in µ, but both considerably underestimate the CT excitation energies for these systems. KS orbital energies are physically meaningful and they are practically useful; if the range-separation parameter is tuned, then good results can be obtained.