Time-dependent theory of the rate of photo-induced electron transfer

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

A novel approach based on constrained real-time time-dependent density functional theory (C-RT-TDDFT) is introduced to accurately evaluate the electronic Hamiltonian coupling associated with photoinduced electron transfer (PIET) using diabatic states that are defined using constrained DFT (C-DFT). In combination with the semiclassical Marcus theory, the photoexcited ET rate for coherently coupled photoexcitation and electron transfer is determined for a given incident wavelength by combining this Hamiltonian coupling with free energy changes and ground state reorganization energies that are obtained using an implicit solvation model. As an application of this method, we consider PIET for the (Ag20-Ag)+ complex as a model of a plasmon-enhanced electron transfer process. Using solar radiation intensity, the fastest PIET rate is found to be induced by an incident wavelength that is distinct (blue-shifted) from the wavelength of strongest plasmon-like excitation associated with the Ag20+ cluster, particularly for large donor-acceptor separations, which suggests a much more efficient coupling Hamiltonian for higher-energy molecular orbitals. Through a comparison between the PIET and absorption cross sections, the quantum efficiency for PIET is found to be a few percent at most at short donor-acceptor distances, and it decays exponentially as they separate.

Original languageEnglish
Pages (from-to)18810-18821
Number of pages12
JournalJournal of Physical Chemistry C
Volume115
Issue number38
DOIs
Publication statusPublished - Sep 29 2011

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electron transfer
Electrons
Hamiltonians
Wavelength
wavelengths
Photoexcitation
Solvation
Molecular orbitals
solar radiation
Solar radiation
Quantum efficiency
photoexcitation
Discrete Fourier transforms
absorption cross sections
Ground state
Free energy
Density functional theory
solvation
radiant flux density
quantum efficiency

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Time-dependent theory of the rate of photo-induced electron transfer. / Chen, Hanning; Ratner, Mark A; Schatz, George C.

In: Journal of Physical Chemistry C, Vol. 115, No. 38, 29.09.2011, p. 18810-18821.

Research output: Contribution to journalArticle

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