U.S. Department of Energy Office of Scientific and Technical Information
Ultrafast Electronic Relaxation through a Conical Intersection: Nonadiabatic Dynamics Disentangled through an Oscillator Strength-Based Diabatization Framework
Journal Article·· Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemistry
Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
Here, we employ surface hopping trajectories to model the short-time dynamics of gas-phase and partially solvated 4-(N,N-dimethylamino)benzonitrile (DMABN), a dual fluorescent molecule that is known to undergo a nonadiabatic transition through a conical intersection. To compare theory vs time-resolved fluorescence measurements, we calculate the mixed quantum–classical density matrix and the ensemble averaged transition dipole moment. We introduce a diabatization scheme based on the oscillator strength to convert the TDDFT adiabatic states into diabatic states of La and Lb character. Somewhat surprisingly, we find that the rate of relaxation reported by emission to the ground state is almost 50% slower than the adiabatic population relaxation. Although our calculated adiabatic rates are largely consistent with previous theoretical calculations and no obvious effects of decoherence are seen, the diabatization procedure introduced here enables an explicit picture of dynamics in the branching plane, raising tantalizing questions about geometric phase effects in systems with dozens of atoms.
Medders, Gregory R., et al. "Ultrafast Electronic Relaxation through a Conical Intersection: Nonadiabatic Dynamics Disentangled through an Oscillator Strength-Based Diabatization Framework." Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, vol. 121, no. 7, Jan. 2017. https://doi.org/10.1021/acs.jpca.6b12120
Medders, Gregory R., Alguire, Ethan C., Jain, Amber, & Subotnik, Joseph E. (2017). Ultrafast Electronic Relaxation through a Conical Intersection: Nonadiabatic Dynamics Disentangled through an Oscillator Strength-Based Diabatization Framework. Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, 121(7). https://doi.org/10.1021/acs.jpca.6b12120
Medders, Gregory R., Alguire, Ethan C., Jain, Amber, et al., "Ultrafast Electronic Relaxation through a Conical Intersection: Nonadiabatic Dynamics Disentangled through an Oscillator Strength-Based Diabatization Framework," Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory 121, no. 7 (2017), https://doi.org/10.1021/acs.jpca.6b12120
@article{osti_1353188,
author = {Medders, Gregory R. and Alguire, Ethan C. and Jain, Amber and Subotnik, Joseph E.},
title = {Ultrafast Electronic Relaxation through a Conical Intersection: Nonadiabatic Dynamics Disentangled through an Oscillator Strength-Based Diabatization Framework},
annote = {Here, we employ surface hopping trajectories to model the short-time dynamics of gas-phase and partially solvated 4-(N,N-dimethylamino)benzonitrile (DMABN), a dual fluorescent molecule that is known to undergo a nonadiabatic transition through a conical intersection. To compare theory vs time-resolved fluorescence measurements, we calculate the mixed quantum–classical density matrix and the ensemble averaged transition dipole moment. We introduce a diabatization scheme based on the oscillator strength to convert the TDDFT adiabatic states into diabatic states of La and Lb character. Somewhat surprisingly, we find that the rate of relaxation reported by emission to the ground state is almost 50% slower than the adiabatic population relaxation. Although our calculated adiabatic rates are largely consistent with previous theoretical calculations and no obvious effects of decoherence are seen, the diabatization procedure introduced here enables an explicit picture of dynamics in the branching plane, raising tantalizing questions about geometric phase effects in systems with dozens of atoms.},
doi = {10.1021/acs.jpca.6b12120},
url = {https://www.osti.gov/biblio/1353188},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {ISSN 1089-5639},
number = {7},
volume = {121},
place = {United States},
publisher = {American Chemical Society},
year = {2017},
month = {01}}
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE; National Science Foundation (NSF)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1353188
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 7 Vol. 121; ISSN 1089-5639
Longuet-Higgins, Hugh Christopher; Öpik, U.; Lecorney Pryce, Maurice Henry
Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 244, Issue 1236, p. 1-16https://doi.org/10.1098/rspa.1958.0022
Journal Article
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Wed Dec 14 23:00:00 EST 2016
· Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
·OSTI ID:1360220