A Perspective on the Relative Merits of Time-Dependent and Time-Independent Density Functional Theory in Studies of the Electron Spectra Due to Transition Metal Complexes. An Illustration Through Applications to Copper Tetrachloride and Plastocyanin

作者：Zhekova Hristina R^*; Seth Michael; Ziegler Tom

来源：International Journal of Quantum Chemistry, 2014, 114(15): 1019-1029.

DOI：10.1002/qua.24624

• adiabatic time-dependent DFT
• orbital relaxation
• self-interaction cancellation
• plastocyanin
• copper tetrachloride

Evaluation of the excitation energies in CuCl42- and plastocyanin was carried out with three different density functional theory (DFT) methods: time-dependent DFT (TDDFT), Delta DFT, and Delta self consistent field (SCF)-DFT. Use was made of two local (local density approximation and BP86), two hybrid (B3LYP and PBE0), and one long-range corrected (LC-BP86) functionals to probe the effect of the exact exchange on the excitation energies. Some well-known deficiencies observed in TDDFT were explained on the basis of lacking orbital relaxation and two-electron terms not considered in adiabatic TDDFT. Delta self consistent field (SCF)-DFT reproduces well the position of the charge-transfer excitations and yields results in best agreement with experiment regardless of the system or functional used. We conclude that the orbital relaxation and proper account of higher-order terms neglected in adiabatic TDDFT are of great importance for the simulation of excitation spectra.

• 出版日期2014-8-5