Nuclear Motion Driven Ultrafast Photodissociative Charge Transfer of the PENNA Cation: An Experimental and Computational Study

Shoutian Sun, Benoit Mignolet, Lin Fan, Wen Li, Raphael D. Levine, Francoise Remacle*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

Ultrafast nuclear driven charge transfer prior to dissociation is an important process in modular systems as was demonstrated experimentally in the bifunctional molecule 2-phenylethyl-N,N-dimethylamine (PENNA) in work by Lehr et al. (J. Phys. Chem. A 2005, 109, 8074). The ultrafast dynamics of PENNA photoexcited to the three lowest electronic states of the cation (D0, D1, and D2) was studied using quantum chemistry and surface hoping. We show that a conical intersection, localized in the Franck-Condon region, between the D0 and the D1 states, leads to an ultrafast charge transfer, computed here to be on a time scale of 65 fs, between the phenyl and the amine charged subunits. On the D0 ground state, the dissociation proceeds on the 60 ps time scale through a 19 kcal/mol late barrier. The computed kinetic energy release is in good agreement with a new experimental measurement of PENNA ionization by an 800 nm 30 fs intense laser pulse.

Original languageEnglish
Pages (from-to)1442-1447
Number of pages6
JournalJournal of Physical Chemistry A
Volume121
Issue number7
DOIs
StatePublished - 23 Feb 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

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