期刊
JOURNAL OF CHEMICAL PHYSICS
卷 130, 期 15, 页码 -出版社
AIP Publishing
DOI: 10.1063/1.3114988
关键词
density functional theory; eigenvalues and eigenfunctions; electric moments; magnetic moments; molecular moments; RPA calculations; Rydberg states; STO calculations; variational techniques
资金
- NSERC
- National Science Foundation
It is shown that it is possible to derive the basic eigenvalue equation of adiabatic time-dependent density functional theory within the Tamm-Dancoff approximation (TD-DFT/TD) from a variational principle. The variational principle is applied to the regular Kohn-Sham formulation of DFT energy expression for a single Slater determinant and leads to the same energy spectrum as TD-DFT/TD. It is further shown that this variational approach affords the same electric and magnetic transition moments as TD-DFT/TD. The variational scheme can also be applied without the Tamm-Dancoff approximation. Practical implementations of TD-DFT are limited to second order response theory which introduces errors in transition energies for charge transfer and Rydberg excitations. It is indicated that higher order terms can be incorporated into the variational approach. It is also discussed how the current variational method is related to traditional DFT schemes based on variational principles such as Delta SCF-DFT, and how they can be combined.
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