Jump to main content
Jump to site search

Issue 5, 2015
Previous Article Next Article

Structural heterogeneity and dynamics of dyes on TiO2: implications for charge transfer across organic–inorganic interfaces

Author affiliations

Abstract

Charge transfer across organic–inorganic interfaces plays a vital role in many important applications. Dye–semiconductor systems are the prototypical such interface and provide an excellent platform for exploring the underlying molecular-level factors that affect charge transfer dynamics and efficiency. Experiments often show multi-exponential electron injection kinetics from adsorbed dyes to a semiconductor substrate, suggesting the presence of interfacial heterogeneity. Nonetheless, both the diversity of interfacial structures and the associated implications for electronic dynamics are poorly understood. In the present work, we examine the effect of structural heterogeneity and dynamics on charge injection (as measured by dye–semiconductor electronic coupling) from plane wave density functional theory and ab initio molecular dynamics calculations on model dye–semiconductor systems. We demonstrate that dye binding motif, conformation, solvation, and corresponding thermal fluctuations significantly affect charge injection kinetics. We suggest that the experimentally observed multi-exponential kinetics likely result not only from an intrinsic heterogeneous distribution of electronic coupling strengths, but also from the conformational or solvent dynamics that in turn modulate the coupling strength and/or band alignment.

Graphical abstract: Structural heterogeneity and dynamics of dyes on TiO2: implications for charge transfer across organic–inorganic interfaces

Back to tab navigation

Supplementary files

Publication details

The article was received on 21 Oct 2014, accepted on 18 Dec 2014 and first published on 18 Dec 2014


Article type: Paper
DOI: 10.1039/C4CP04814H
Author version
available:
Download author version (PDF)
Phys. Chem. Chem. Phys., 2015,17, 3731-3740

  •   Request permissions

    Structural heterogeneity and dynamics of dyes on TiO2: implications for charge transfer across organic–inorganic interfaces

    J. R. Christianson and J. R. Schmidt, Phys. Chem. Chem. Phys., 2015, 17, 3731
    DOI: 10.1039/C4CP04814H

Search articles by author

Spotlight

Advertisements