The ultrafast decay dynamics of 4-(N,N-dimethylamino)benzonitrile (DMABN) following photoexcitation was studied with the ab initio multiple spawning (AIMS) method, combined with GPU-accelerated linear-response time-dependent density functional theory (LR-TDDFT). We validate the LR-TDDFT method for this case and then present a detailed analysis of the first ≈200 fs of DMABN excited-state dynamics. Almost complete nonadiabatic population transfer from S2 (the initially populated bright state) to S1 takes place in less than 50 fs, without significant torsion of the dimethylamino (DMA) group. Significant torsion of the DMA group is only observed after the nuclear wavepacket reaches S1 and acquires locally excited electronic character. Here, our results show that torsion of the DMA group is not prerequisite for nonadiabatic transitions in DMABN, although such motion is indeed relevant on the lowest excited state (S1).
Curchod, Basile F. E., et al. "Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs." Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, vol. 121, no. 1, Dec. 2016. https://doi.org/10.1021/acs.jpca.6b09962
Curchod, Basile F. E., Sisto, Aaron, & Martinez, Todd J. (2016). Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs. Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, 121(1). https://doi.org/10.1021/acs.jpca.6b09962
Curchod, Basile F. E., Sisto, Aaron, and Martinez, Todd J., "Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs," Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory 121, no. 1 (2016), https://doi.org/10.1021/acs.jpca.6b09962
@article{osti_1360220,
author = {Curchod, Basile F. E. and Sisto, Aaron and Martinez, Todd J.},
title = {Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs},
annote = {The ultrafast decay dynamics of 4-(N,N-dimethylamino)benzonitrile (DMABN) following photoexcitation was studied with the ab initio multiple spawning (AIMS) method, combined with GPU-accelerated linear-response time-dependent density functional theory (LR-TDDFT). We validate the LR-TDDFT method for this case and then present a detailed analysis of the first ≈200 fs of DMABN excited-state dynamics. Almost complete nonadiabatic population transfer from S2 (the initially populated bright state) to S1 takes place in less than 50 fs, without significant torsion of the dimethylamino (DMA) group. Significant torsion of the DMA group is only observed after the nuclear wavepacket reaches S1 and acquires locally excited electronic character. Here, our results show that torsion of the DMA group is not prerequisite for nonadiabatic transitions in DMABN, although such motion is indeed relevant on the lowest excited state (S1).},
doi = {10.1021/acs.jpca.6b09962},
url = {https://www.osti.gov/biblio/1360220},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {ISSN 1089-5639},
number = {1},
volume = {121},
place = {United States},
publisher = {American Chemical Society},
year = {2016},
month = {12}}
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1360220
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: 1 Vol. 121; ISSN 1089-5639
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Mon Oct 20 00:00:00 EDT 2014
· Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
·OSTI ID:1233235
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