Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs

Curchod, Basile F.E.; Sisto, Aaron; Martínez, Todd J.

doi:10.1021/acs.jpca.6b09962

Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs

Curchod, Basile F.E.; Sisto, Aaron; Martínez, Todd J.

Authors

Dr Basile Curchod basile.f.curchod@durham.ac.uk
Academic Visitor

Aaron Sisto

Todd J. Martínez

Abstract

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. 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).

Citation

Curchod, B. F., Sisto, A., & Martínez, T. J. (2017). Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs. The Journal of Physical Chemistry A, 121(1), 265-276. https://doi.org/10.1021/acs.jpca.6b09962

Journal Article Type	Article
Acceptance Date	Oct 2, 2016
Online Publication Date	Dec 15, 2016
Publication Date	Jan 12, 2017
Deposit Date	Nov 6, 2017
Publicly Available Date	Dec 15, 2017
Journal	The Journal of Physical Chemistry A
Print ISSN	1089-5639
Electronic ISSN	1520-5215
Publisher	American Chemical Society
Peer Reviewed	Peer Reviewed
Volume	121
Issue	1
Pages	265-276
DOI	https://doi.org/10.1021/acs.jpca.6b09962

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.6b09962.