Ab initio nonadiabatic molecular dynamics of the ultrafast electron injection across the alizarin-TiO2 interface

被引:242
作者
Duncan, WR [1 ]
Stier, WM [1 ]
Prezhdo, OV [1 ]
机构
[1] Univ Washington, Dept Chem, Seattle, WA 98195 USA
关键词
D O I
10.1021/ja042156v
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The observed 6-fs photoinduced electron transfer (ET) from the alizarin chromophore into the TiO2 surface is investigated by ab initio nonadiabatic (NA) molecular dynamics in real time and at the atomistic level of detail. The system derives from the dye-sensitized semiconductor Gratzel cell and addresses the problems of an organic/inorganic interface that are commonly encountered in photovoltaics, photochemistry, and molecular electronics. In contrast to the typical Gratzel cell systems, where molecular donors are in resonance with a high density of semiconductor acceptor states, TiO2 sensitized with alizarin presents a novel case in which the molecular photoexcited state is at the edge of the conduction band (CB). The high level ab initio analysis of the optical absorption spectrum supports this observation. Thermal fluctuations of atomic coordinates are particularly important both in generating a nonuniform distribution of photoexcited states and in driving the ET process. The NA simulation resolves the controversy regarding the origin of the ultrafast ET by showing that although ultrafast transfer is possible with the NA mechanism, it proceeds mostly adiabatically in the alizarin-TiO2 system. The simulation indicates that the electron is injected into a localized surface state within 8 fs and spreads into the bulk on a 100-fs or longer time scale. The molecular architecture seen in the alizarin-TiO2 system permits efficient electron injection into the edge of the CB by an adiabatic mechanism without the energy loss associated with injection high into the CB by a NA process.
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页码:7941 / 7951
页数:11
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共 107 条
[61]  
O'Regan B, 2000, ADV MATER, V12, P1263, DOI 10.1002/1521-4095(200009)12:17<1263::AID-ADMA1263>3.0.CO
[62]  
2-T
[63]   Bi-isonicotinic acid on rutile (110): calculated molecular and electronic structure [J].
Odelius, M ;
Persson, P ;
Lunell, S .
SURFACE SCIENCE, 2003, 529 (1-2) :47-58
[64]   Electronic excitations: density-functional versus many-body Green's-function approaches [J].
Onida, G ;
Reining, L ;
Rubio, A .
REVIEWS OF MODERN PHYSICS, 2002, 74 (02) :601-659
[65]   A LOW-COST, HIGH-EFFICIENCY SOLAR-CELL BASED ON DYE-SENSITIZED COLLOIDAL TIO2 FILMS [J].
OREGAN, B ;
GRATZEL, M .
NATURE, 1991, 353 (6346) :737-740
[66]   Photoinduced electron transfer between a carotenoid and TiO2 nanoparticle [J].
Pan, J ;
Benkö, G ;
Xu, YH ;
Pascher, T ;
Sun, LC ;
Sundström, V ;
Polívka, T .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (46) :13949-13957
[67]   Generalized gradient approximation for the exchange-correlation hole of a many-electron system [J].
Perdew, JP ;
Burke, K ;
Wang, Y .
PHYSICAL REVIEW B, 1996, 54 (23) :16533-16539
[68]   Quantum chemical study of photoinjection processes in dye-sensitized TiO2 nanoparticles [J].
Persson, P ;
Bergström, R ;
Lunell, S .
JOURNAL OF PHYSICAL CHEMISTRY B, 2000, 104 (44) :10348-10351
[69]   Binding of bi-isonicotinic acid to anatase TiO2 (101) [J].
Persson, P ;
Lunell, S .
SOLAR ENERGY MATERIALS AND SOLAR CELLS, 2000, 63 (02) :139-148
[70]   Quantum chemical prediction of the adsorption conformations and dynamics at HCOOH-covered ZnO(10(1)over-bar-0) surfaces [J].
Persson, P ;
Lunell, S ;
Ojamäe, L .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2002, 89 (03) :172-180