Crucial Role of Nuclear Dynamics for Electron Injection in a Dye-Semiconductor Complex.
We investigate the electron injection from a terrylene-based chromophore to the TiO2 semiconductor bridged by a recently proposed phenyl-amide-phenyl molecular rectifier. The mechanism of electron transfer is studied by means of quantum dynamics simulations using an extended Hückel Hamiltonian. It is found that the inclusion of the nuclear motion is necessary to observe the photoinduced electron transfer. In particular, the fluctuations of the dihedral angle between the terrylene and the phenyl ring modulate the localization and thus the electronic coupling between the donor and acceptor states involved in the injection process. The electron propagation shows characteristic oscillatory features that correlate with interatomic distance fluctuations in the bridge, which are associated with the vibrational modes driving the process. The understanding of such effects is important for the design of functional dyes with optimal injection and rectification properties.
†Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2300 RA, Leiden, The Netherlands.
Adriano
A
Monti
§Theoretical Division, Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, New Mexico 87545, United States.
Christian F A
CF
Negre
‡Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520, United States.
Victor S
VS
Batista
∥Department of Physics, Universidade Federal de Santa Catarina, Florianópolis, Santa Catarina 88040-900, Brazil.
Luis G C
LG
Rego
†Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2300 RA, Leiden, The Netherlands.
Huub J M
HJ
de Groot
†Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2300 RA, Leiden, The Netherlands.
Francesco
F
Buda
dye-sensitized solar cells; interfacial electron transfer; quantum coherence; tight-binding nonadiabatic dynamics