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
Article first published online: 6 FEB 2014
Copyright © 2014 Wiley Periodicals, Inc.
International Journal of Quantum Chemistry
Special Issue: VIIIth Congress of the International Society for Theoretical Chemical Physics
Volume 114, Issue 15, pages 1019–1029, 5 August 2014
How to Cite
How to cite this article: Int. J. Quantum Chem. 2014, 114, 1019–1029. DOI: 10.1002/qua.24624, , .
- Issue published online: 16 JUN 2014
- Article first published online: 6 FEB 2014
- Manuscript Accepted: 8 JAN 2014
- Manuscript Revised: 19 DEC 2013
- Manuscript Received: 14 NOV 2013
- University of Calgary
- adiabatic time-dependent DFT;
- orbital relaxation;
- self-interaction cancellation;
- copper tetrachloride
Evaluation of the excitation energies in and plastocyanin was carried out with three different density functional theory (DFT) methods: time-dependent DFT (TDDFT), ΔDFT, and Δself 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. Δself 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. © 2014 Wiley Periodicals, Inc.