Nonadiabatic dynamics and simulation of time resolved photoelectron spectra within time-dependent density functional theory: Ultrafast photoswitching in benzylideneaniline

Journal Article · Tue Oct 28 00:00:00 EDT 2008 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3000012· OSTI ID:21254781

Mitric, Roland; Werner, Ute; Bonacic-Koutecky, Vlasta ^[1]

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1. Institut fuer Chemie, Humboldt-Universitaet zu Berlin, Brook-Taylor-Strasse 2, D-12489 Berlin (Germany)

We present a theoretical approach for the nonadiabatic dynamics 'on the fly' based on the combination of the time-dependent density functional theory (TDDFT) with Tully's stochastic surface hopping method. Our formulation is based on localized Gaussian basis sets and is suitable for the simulation of ultrafast processes in complex molecular systems including all degrees of freedom. Our approach is used for the simulation of time resolved photoelectron spectra in the framework of the Wigner distribution approach. In order to illustrate the scope of the method, we study the ultrafast photoswitching dynamics of the prototype Schiff base benzylideneaniline (BAN). The nonradiative lifetime of the S{sub 1} state of BAN is determined to be {approx}200 fs. The mechanism of the photoisomerization has been investigated and a connection between the time resolved photoelectron signal and the underlying nonadiabatic processes has been established.

• OSTI ID: 21254781
• Journal Information: Journal of Chemical Physics, Vol. 129, Issue 16; Other Information: DOI: 10.1063/1.3000012; (c) 2008 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMINES
AROMATICS
DEGREES OF FREEDOM
DENSITY FUNCTIONAL METHOD
GAUSSIAN PROCESSES
ISOMERIZATION
PHOTOCHEMISTRY
PHOTOELECTRON SPECTROSCOPY
REACTION KINETICS
SCHIFF BASES
SIMULATION
SPECTRA
STOCHASTIC PROCESSES
TIME DEPENDENCE
TIME RESOLUTION
WIGNER DISTRIBUTION