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Nonadiabatic Dynamics of a Truncated Indigo Model

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http://pubman.mpdl.mpg.de/cone/persons/resource/persons58498

Cui,  Ganglong
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons59045

Thiel,  Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Cui, G., & Thiel, W. (2012). Nonadiabatic Dynamics of a Truncated Indigo Model. Physical Chemistry Chemical Physics, 14(35), 12378-12384. doi:10.1039/c2cp41867c.


Cite as: http://hdl.handle.net/11858/00-001M-0000-000E-E6C3-A
Abstract
Indigo (1) is stable when exposed to ultraviolet light. We employ electronic structure calculations and nonadiabatic trajectory surface-hopping dynamics simulations to study the photoinduced processes and the photoprotection mechanism of an indigo model, bispyrroleindigo (2). Consistent with recent static ab initio calculations on 1 and 2 (Phys. Chem. Chem. Phys., 2011, 13, 1618), we find an efficient deactivation process that proceeds as follows. After vertical photoexcitation, the S1(ππ*) state undergoes an essentially barrierless intramolecular single proton transfer and relaxes to the minimum of an S1 tautomer, which is structurally and energetically close to a nearby conical intersection that acts as a funnel to the S0 state; after this internal conversion, a reverse single hydrogen transfer leads back to the equilibrium structure of the most stable S0 tautomer. This deactivation process is completely dominant in our semiempirical OM2/MRCI nonadiabatic dynamics simulations. The other two mechanisms considered previously, namely excited-state intramolecular double proton transfer and trans–cis double bond isomerization, are not seen in any of the 325 trajectories of the present surface-hopping simulations. On the basis of the computed time-dependent populations of the S1 state, we estimate an S1 lifetime of about 700 fs for 2 in the gas phase.