A molecular movie of ultrafast singlet fission.

Autor: Schnedermann C; Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge, CB3 0HE, UK. cs2002@cam.ac.uk.; Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, OX1 3QZ, UK. cs2002@cam.ac.uk., Alvertis AM; Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge, CB3 0HE, UK., Wende T; Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, OX1 3QZ, UK., Lukman S; Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge, CB3 0HE, UK.; Institute of Materials Research and Engineering, Agency for Science Technology and Research (A*STAR), 2 Fusionopolis Way, Singapore, 138634, Singapore., Feng J; Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore., Schröder FAYN; Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge, CB3 0HE, UK., Turban DHP; Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge, CB3 0HE, UK., Wu J; Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore., Hine NDM; Department of Physics, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK., Greenham NC; Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge, CB3 0HE, UK., Chin AW; Centre National de la Recherce Scientifique, Institute des Nanosciences de Paris, Sorbonne Universite, Paris, France., Rao A; Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge, CB3 0HE, UK., Kukura P; Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, OX1 3QZ, UK., Musser AJ; Department of Physics and Astronomy, University of Sheffield, Hounsfield Road, Sheffield, S3 7RH, UK. ajm557@cornell.edu.; Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, NY, 14853, USA. ajm557@cornell.edu.
Jazyk: angličtina
Zdroj: Nature communications [Nat Commun] 2019 Sep 16; Vol. 10 (1), pp. 4207. Date of Electronic Publication: 2019 Sep 16.
DOI: 10.1038/s41467-019-12220-7
Abstrakt: The complex dynamics of ultrafast photoinduced reactions are governed by their evolution along vibronically coupled potential energy surfaces. It is now often possible to identify such processes, but a detailed depiction of the crucial nuclear degrees of freedom involved typically remains elusive. Here, combining excited-state time-domain Raman spectroscopy and tree-tensor network state simulations, we construct the full 108-atom molecular movie of ultrafast singlet fission in a pentacene dimer, explicitly treating 252 vibrational modes on 5 electronic states. We assign the tuning and coupling modes, quantifying their relative intensities and contributions, and demonstrate how these modes coherently synchronise to drive the reaction. Our combined experimental and theoretical approach reveals the atomic-scale singlet fission mechanism and can be generalized to other ultrafast photoinduced reactions in complex systems. This will enable mechanistic insight on a detailed structural level, with the ultimate aim to rationally design molecules to maximise the efficiency of photoinduced reactions.
Databáze: MEDLINE