Analytical energy gradients of Coulomb-attenuated time-dependent density functional methods for excited states

Authors

  • Kiet A. Nguyen,

    Corresponding author
    1. Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, OH 45433
    2. UES, Inc., Dayton, OH 45432
    • Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, OH 45433
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  • Paul N. Day,

    1. Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, OH 45433
    2. General Dynamics Information Technology, Inc., Dayton, OH 45431
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  • Ruth Pachter

    Corresponding author
    1. Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, OH 45433
    • Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, OH 45433
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Abstract

We present an implementation and validation of the analytical energy gradient of time-dependent density functional theory (TDDFT) using Coulomb-attenuated (CA) functionals for excited state energies, dipole moments, geometries, and vibrational frequencies. The CA-TDDFT gradient is based on the previous long-range corrected TDDFT of (Chiba et al. J Chem Phys 2006, 124, 144106) and the Z-vector formalism of (Furche and Ahlrichs J Chem Phys 2002, 117, 7433). Geometry optimization using CA-TDDFT was carried out for molecules (substituted stilbenes and coumarins) having intramolecular charge-transfer excited states and for a series of small molecules (CO, HCN, CH2O, CH2S, CCl2, C2H2, trans-(CHO)2). We assess the results of the CA functionals, the long-range corrected LC-BLYP functional, and the B3LYP hybrid functional, by comparing to accurate experimental data. The results highlight the applicabilty of different functionals for excited state properties. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010

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