Analytical second derivatives of excited-state energy within the time-dependent density functional theory coupled with a conductor-like polarizable continuum model

作者：Liu, Jie^*; Liang, WanZhen

来源：Journal of Chemical Physics, 2013, 138(2): 024101.

DOI：10.1063/1.4773397

• TAMM-DANCOFF APPROXIMATION
• GREEN FLUORESCENT PROTEIN
• ANISOTROPIC DIELECTRICS
• SOLVATION MODELS
• INFRARED-SPECTRA
• SOLVENT
• IMPLEMENTATION
• EQUATIONS
• FLUORENONE
• GRADIENTS

This work extends our previous works [J. Liu and W. Z. Liang, J. Chem. Phys. 135, 014113 (2011); J. Liu and W. Z. Liang, J. Chem. Phys. 135, 184111 (2011)] on analytical excited-state Hessian within the framework of time-dependent density functional theory (TDDFT) to couple with a conductor-like polarizable continuum model (CPCM). The formalism, implementation, and application of analytical first and second energy derivatives of TDDFT/CPCM excited state with respect to the nuclear and electric perturbations are presented. Their performances are demonstrated by the calculations of excitation energies, excited-state geometries, and harmonic vibrational frequencies for a number of benchmark systems. The calculated results are in good agreement with the corresponding experimental data or other theoretical calculations, indicating the reliability of the current computer implementation of the developed algorithms. Then we made some preliminary applications to calculate the resonant Raman spectrum of 4-hydroxybenzylidene-2,3-dimethyl-imidazolinone in ethanol solution and the infrared spectra of ground and excited states of 9-fluorenone in methanol solution.

• 出版日期2013-1-14
• 单位厦门大学; 中国科学技术大学