TY - JOUR
T1 - Nuclear Motion Driven Ultrafast Photodissociative Charge Transfer of the PENNA Cation
T2 - An Experimental and Computational Study
AU - Sun, Shoutian
AU - Mignolet, Benoit
AU - Fan, Lin
AU - Li, Wen
AU - Levine, Raphael D.
AU - Remacle, Francoise
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/2/23
Y1 - 2017/2/23
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85018638836&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.6b12310
DO - 10.1021/acs.jpca.6b12310
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C2 - 28135094
AN - SCOPUS:85018638836
SN - 1089-5639
VL - 121
SP - 1442
EP - 1447
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 7
ER -