Real-time non-adiabatic modeling of time-resolved pump-probe spectra using time-dependent density functional theory

ORAL

Abstract

We model non-adiabatic excited state decay of organic molecules using time-dependent density functional theory surface hopping [1,2]. Based on the surface hopping trajectories we compute time-resolved transient absorption spectra [3], time-dependent photoelectron ionization spectra [4], and time-depnednt circular dichroism spectra. Calculated spectra and molecular structures are used to unravel features in experimental spectra that are not directly accessible from experiments. Our trajectories allow to analyze parallel decay channels separately and asses the effect of substituents on the excited state decay and stereoselectivity of electrocyclic reactions. Applications include provitamin D and its model systems cyclohexadiene, alpha-terpinene, and phellandrene. [1] E. Tapavicza, A. M. Meyer, and F. Furche. Unravelling the details of vitamin D photosynthesis by non-adiabatic molecular dynamics simulations. Phys. Chem. Chem. Phys., 13:20986, 2011. [2] E. Tapavicza, G. D. Bellchambers, J. C. Vincent, and F. Furche. Ab initio non-adiabatic molecular dynamics. Phys. Chem. Chem. Phys., 15:18336–18348, 2013. [3] B. C. Arruda, J. Peng, B. Smith, K. G. Spears, and R. J. Sension. Photochemical ring-opening and ground state relaxation in alpha-terpinene with comparison to provitamin D3. J. Phys. Chem. B, 117(16):4696–4704, 2013. [4] Schalk, O.; Boguslavskiy, A. E.; Stolow, A. Two-Photon Excited State Dynamics of Dark Valence, Rydberg, and Superexcited States in 1,3-Butadiene. J. Phys. Chem. Lett., 5, 560-565, 2014.

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Authors

  • Enrico Tapavicza

    California State University, Long Beach

  • Chi-Yu Hu

    University of California - Berkeley, National Institute for Materials Science, Caifornia State University, Long Beach, University of Michigan, Stockholm University, California State University, Long Beach, Utrecht University, Carl von Ossietzky University of Oldenburg, Germany, Hartnell Community College, Department of Physics, Stockholm University, GRAPPA, University of Amsterdam, Paul Scherrer Institute, Switzerland, California State University, Fresno, California State University Long Beach, Cal State Univ- Long Beach, University of Nevada, Reno, University of Rogensberg, Germany, Tribhuvan University, Nepal, University of Victoria and Perimeter Institute for Theoretical Physics, Institute of Physics, Jagiellonian University, Helmholtz Institute Mainz, Johannes Gutenberg University, Physics Department of the University of Nevada, Reno, Universita del Sannio, Cal Tech, California State University, Los Angeles, Univ of California - San Diego, UC Berkeley, Lawrence Livermore National Laboratory, Department of Physics & Astronomy, University of California, Irvine 92617, Department of Chemistry and of Physics & Astronomy, University of California, Irvine 92617, SLAC National Laboratory, Humboldt State University, Physics Department, University of Nevada, Reno, Univ of California - Merced

  • Chi-Yu Hu

    University of California - Berkeley, National Institute for Materials Science, Caifornia State University, Long Beach, University of Michigan, Stockholm University, California State University, Long Beach, Utrecht University, Carl von Ossietzky University of Oldenburg, Germany, Hartnell Community College, Department of Physics, Stockholm University, GRAPPA, University of Amsterdam, Paul Scherrer Institute, Switzerland, California State University, Fresno, California State University Long Beach, Cal State Univ- Long Beach, University of Nevada, Reno, University of Rogensberg, Germany, Tribhuvan University, Nepal, University of Victoria and Perimeter Institute for Theoretical Physics, Institute of Physics, Jagiellonian University, Helmholtz Institute Mainz, Johannes Gutenberg University, Physics Department of the University of Nevada, Reno, Universita del Sannio, Cal Tech, California State University, Los Angeles, Univ of California - San Diego, UC Berkeley, Lawrence Livermore National Laboratory, Department of Physics & Astronomy, University of California, Irvine 92617, Department of Chemistry and of Physics & Astronomy, University of California, Irvine 92617, SLAC National Laboratory, Humboldt State University, Physics Department, University of Nevada, Reno, Univ of California - Merced

  • Chi-Yu Hu

    University of California - Berkeley, National Institute for Materials Science, Caifornia State University, Long Beach, University of Michigan, Stockholm University, California State University, Long Beach, Utrecht University, Carl von Ossietzky University of Oldenburg, Germany, Hartnell Community College, Department of Physics, Stockholm University, GRAPPA, University of Amsterdam, Paul Scherrer Institute, Switzerland, California State University, Fresno, California State University Long Beach, Cal State Univ- Long Beach, University of Nevada, Reno, University of Rogensberg, Germany, Tribhuvan University, Nepal, University of Victoria and Perimeter Institute for Theoretical Physics, Institute of Physics, Jagiellonian University, Helmholtz Institute Mainz, Johannes Gutenberg University, Physics Department of the University of Nevada, Reno, Universita del Sannio, Cal Tech, California State University, Los Angeles, Univ of California - San Diego, UC Berkeley, Lawrence Livermore National Laboratory, Department of Physics & Astronomy, University of California, Irvine 92617, Department of Chemistry and of Physics & Astronomy, University of California, Irvine 92617, SLAC National Laboratory, Humboldt State University, Physics Department, University of Nevada, Reno, Univ of California - Merced

  • Chi-Yu Hu

    University of California - Berkeley, National Institute for Materials Science, Caifornia State University, Long Beach, University of Michigan, Stockholm University, California State University, Long Beach, Utrecht University, Carl von Ossietzky University of Oldenburg, Germany, Hartnell Community College, Department of Physics, Stockholm University, GRAPPA, University of Amsterdam, Paul Scherrer Institute, Switzerland, California State University, Fresno, California State University Long Beach, Cal State Univ- Long Beach, University of Nevada, Reno, University of Rogensberg, Germany, Tribhuvan University, Nepal, University of Victoria and Perimeter Institute for Theoretical Physics, Institute of Physics, Jagiellonian University, Helmholtz Institute Mainz, Johannes Gutenberg University, Physics Department of the University of Nevada, Reno, Universita del Sannio, Cal Tech, California State University, Los Angeles, Univ of California - San Diego, UC Berkeley, Lawrence Livermore National Laboratory, Department of Physics & Astronomy, University of California, Irvine 92617, Department of Chemistry and of Physics & Astronomy, University of California, Irvine 92617, SLAC National Laboratory, Humboldt State University, Physics Department, University of Nevada, Reno, Univ of California - Merced

  • Chi-Yu Hu

    University of California - Berkeley, National Institute for Materials Science, Caifornia State University, Long Beach, University of Michigan, Stockholm University, California State University, Long Beach, Utrecht University, Carl von Ossietzky University of Oldenburg, Germany, Hartnell Community College, Department of Physics, Stockholm University, GRAPPA, University of Amsterdam, Paul Scherrer Institute, Switzerland, California State University, Fresno, California State University Long Beach, Cal State Univ- Long Beach, University of Nevada, Reno, University of Rogensberg, Germany, Tribhuvan University, Nepal, University of Victoria and Perimeter Institute for Theoretical Physics, Institute of Physics, Jagiellonian University, Helmholtz Institute Mainz, Johannes Gutenberg University, Physics Department of the University of Nevada, Reno, Universita del Sannio, Cal Tech, California State University, Los Angeles, Univ of California - San Diego, UC Berkeley, Lawrence Livermore National Laboratory, Department of Physics & Astronomy, University of California, Irvine 92617, Department of Chemistry and of Physics & Astronomy, University of California, Irvine 92617, SLAC National Laboratory, Humboldt State University, Physics Department, University of Nevada, Reno, Univ of California - Merced

  • Chi-Yu Hu

    University of California - Berkeley, National Institute for Materials Science, Caifornia State University, Long Beach, University of Michigan, Stockholm University, California State University, Long Beach, Utrecht University, Carl von Ossietzky University of Oldenburg, Germany, Hartnell Community College, Department of Physics, Stockholm University, GRAPPA, University of Amsterdam, Paul Scherrer Institute, Switzerland, California State University, Fresno, California State University Long Beach, Cal State Univ- Long Beach, University of Nevada, Reno, University of Rogensberg, Germany, Tribhuvan University, Nepal, University of Victoria and Perimeter Institute for Theoretical Physics, Institute of Physics, Jagiellonian University, Helmholtz Institute Mainz, Johannes Gutenberg University, Physics Department of the University of Nevada, Reno, Universita del Sannio, Cal Tech, California State University, Los Angeles, Univ of California - San Diego, UC Berkeley, Lawrence Livermore National Laboratory, Department of Physics & Astronomy, University of California, Irvine 92617, Department of Chemistry and of Physics & Astronomy, University of California, Irvine 92617, SLAC National Laboratory, Humboldt State University, Physics Department, University of Nevada, Reno, Univ of California - Merced

  • Chi-Yu Hu

    University of California - Berkeley, National Institute for Materials Science, Caifornia State University, Long Beach, University of Michigan, Stockholm University, California State University, Long Beach, Utrecht University, Carl von Ossietzky University of Oldenburg, Germany, Hartnell Community College, Department of Physics, Stockholm University, GRAPPA, University of Amsterdam, Paul Scherrer Institute, Switzerland, California State University, Fresno, California State University Long Beach, Cal State Univ- Long Beach, University of Nevada, Reno, University of Rogensberg, Germany, Tribhuvan University, Nepal, University of Victoria and Perimeter Institute for Theoretical Physics, Institute of Physics, Jagiellonian University, Helmholtz Institute Mainz, Johannes Gutenberg University, Physics Department of the University of Nevada, Reno, Universita del Sannio, Cal Tech, California State University, Los Angeles, Univ of California - San Diego, UC Berkeley, Lawrence Livermore National Laboratory, Department of Physics & Astronomy, University of California, Irvine 92617, Department of Chemistry and of Physics & Astronomy, University of California, Irvine 92617, SLAC National Laboratory, Humboldt State University, Physics Department, University of Nevada, Reno, Univ of California - Merced