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Analytical derivative techniques for TDDFT excited-state properties: Theory and application

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Abstract

We review our recent work on the methodology development of the excited-state properties for the molecules in vacuum and liquid solution. The general algorithms of analytical energy derivatives for the specific properties such as the first and second geometrical derivatives and IR/Raman intensities are demonstrated in the framework of the time-dependent density functional theory (TDDFT). The performance of the analytical approaches on the calculation of excited-state energy Hessian has also been shown. It is found that the analytical approaches are superior to the finite-difference method on the computational accuracy and efficiency. The computational cost for a TDDFT excited-state Hessian calculation is only 2–3 times as that for the DFT ground-state Hessian calculation. With the low computational complexity of the developed analytical approaches, it becomes feasible to realize the large-scale numerical calculations on the excited-state vibrational frequencies, vibrational spectroscopies and the electronic-structure parameters which enter the spectrum calculations of electronic absorption and emission, and resonance Raman spectroscopies for medium-to large-sized systems.

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Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces; Collaborative Innovation Center of Chemistry for Energy Materials, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry; Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    DanPing Chen, Qiao Zeng & WanZhen Liang

  2. Hefei National Laboratory for Physical Science at Microscale, University of Science and Technology of China, Hefei, 230026, China

    Jie Liu

  3. Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026, China

    HuiLi Ma

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  1. DanPing Chen
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  2. Jie Liu
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  3. HuiLi Ma
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  5. WanZhen Liang
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Correspondence to WanZhen Liang.

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Chen, D., Liu, J., Ma, H. et al. Analytical derivative techniques for TDDFT excited-state properties: Theory and application. Sci. China Chem. 57, 48–57 (2014). https://doi.org/10.1007/s11426-013-5006-6

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