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  Early Events in the Nonadiabatic Relaxation Dynamics of 4‑(N,N‑Dimethylamino)benzonitrile

Kochman, M., Tajti, A., Morrison, C. A., & Miller, R. J. D. (2015). Early Events in the Nonadiabatic Relaxation Dynamics of 4‑(N,N‑Dimethylamino)benzonitrile. Journal of Chemical Theory and Computation, 11(3), 1118-1128. doi:10.1021/ct5010609.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0024-C442-A Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002A-FB5C-9
Genre: Journal Article

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http://dx.doi.org/10.1021/ct5010609 (Publisher version)
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 Creators:
Kochman, Michal1, Author              
Tajti, Attila2, Author
Morrison, Carole A.3, Author
Miller, R. J. Dwayne1, Author              
Affiliations:
1Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938288              
2Institute of Chemistry, Eötvös Loránd University, Budapest 1053, Hungary, ou_persistent22              
3School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, Scotland EH9 3FJ, ou_persistent22              

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 Abstract: 4-(N,N-Dimethylamino)benzonitrile (DMABN) is the archetypal system for dual fluorescence. Several past studies, both experimental and theoretical, have examined the mechanism of its relaxation in the gas phase following photoexcitation to the S2 state, without converging to a single description. In this contribution, we report first-principles simulations of the early events involved in this process performed using the nonadiabatic trajectory surface hopping (TSH) approach in combination with the ADC(2) electronic structure method. ADC(2) is verified to reproduce the ground- and excited-state structures of DMABN in reasonably close agreement with previous theoretical benchmarks. The TSH simulations predict that internal conversion from the S2 state to the S1 takes place as early as 8.5 fs, on average, after the initial photoexcitation, and with no significant torsion of the dimethylamino group relative to the aromatic ring. As evidenced by supporting EOM-CCSD calculations, the population transfer from S2 to S1 can be attributed to the skeletal deformation modes of the aromatic ring and the stretching of the ring-dimethylamino nitrogen bond. The non- or slightly twisted locally excited structure is the predominant product of the internal conversion, and the twisted intramolecular charge transfer structure is formed through equilibration with the locally excited structure with no change of adiabatic state. These findings point toward a new interpretation of data from previous time-resolved experiments.

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Language(s): eng - English
 Dates: 2014-11-262015-01-262015-03-10
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1021/ct5010609
 Degree: -

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Title: Journal of Chemical Theory and Computation
  Other : J. Chem. Theory Comput.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 11 (3) Sequence Number: - Start / End Page: 1118 - 1128 Identifier: Other: 1549-9618
CoNE: /journals/resource/111088195283832