Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs

作者：Curchod Basile F E; Sisto Aaron; Martinez Todd J

来源：Journal of Physical Chemistry A, 2017, 121(1): 265-276.

DOI：10.1021/acs.jpca.6b09962

The ultrafast decay dynamics of 4-(N,N-dirnethylamino)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 approximate to 200 fs of DMABN excited-state dynamics. Almost complete nonadiabatic popiilation transfer from S-2 (the initially ptipulated bright state) to S-1 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 S-1 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 (S-1).

• 出版日期2017-1-12