Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 153, Issue 8, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.5140243
Keywords
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Funding
- Academia Sinica
- Ministry of Science and Technology of Taiwan [105-2113-M001-009-MY4, MOST107-2628-M002-005-MY3]
- National Taiwan University [NTUCDP-105R7818]
- Academia Sinica Distinguished Postdoctoral Fellowship
- [AS-IA-106-M01]
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The time-dependent density functional theory (TDDFT) has been broadly used to investigate the excited-state properties of various molecular systems. However, the current TDDFT heavily relies on outcomes from the corresponding ground-state DFT calculations, which may be prone to errors due to the lack of proper treatment in the non-dynamical correlation effects. Recently, thermally assisted-occupation DFT (TAO-DFT) [J.-D. Chai, J. Chem. Phys. 136, 154104 (2012)], a DFT with fractional orbital occupations, was proposed, explicitly incorporating the non-dynamical correlation effects in the ground-state calculations with low computational complexity. In this work, we develop TDTAO-DFT, which is a TD, linear-response theory for excited states within the framework of TAO-DFT. With tests on the excited states of H-2, the first triplet excited state (1(3) Sigma(+)(u)) was described well, with non-imaginary excitation energies. TDTAO-DFT also yields zero singlet-triplet gap in the dissociation limit for the ground singlet (1(1)Sigma(+)(g)) and the first triplet state (1(3) Sigma(+)(u)). In addition, as compared to traditional TDDFT, the overall excited-state potential energy surfaces obtained from TDTAO-DFT are generally improved and better agree with results from the equation-of-motion coupled-cluster singles and doubles. Published under license by AIP Publishing.
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