Theoretical calculation of the photo-induced electron transfer rate between a gold atom and a gold cation solvated in CCl4

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Abstract

A theoretical calculation was performed to evaluate the photo-induced electron transfer (PIET) rate between a gold atom and a gold ion solvated in carbon tetrachloride (CCl4) in the framework of Marcus electron transfer (ET) theory, including both solvent reorganization effects and electronic wavefunction coupling between the ET diabatic states. A novel component of this work involves calculation of the electronic coupling strength using a recently developed constrained real-time time-dependent density-functional-theory (CRT-TDDFT) method. It is found that the PIET rate reaches its maximum value at the electronic resonance wavelength regardless of the inter-particle separation, suggesting a strong correlation between PIET and light absorption. In comparison with thermally activated electron transfer (TAET) at room temperature, light irradiation is demonstrated to be much more efficient than thermal fluctuations in promoting long-range ET, at least for the most common situations, when the light travelling substantially exceeds thermal energy. This work is the first step towards a quantum theory of plasmon enhanced electron transfer, and the theory can also be used to calculate electron transfer rates quite generally for condensed phase problems.

Original languageEnglish
Pages (from-to)143-147
Number of pages5
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume221
Issue number2-3
DOIs
Publication statusPublished - Jun 25 2011

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Gold
Cations
electron transfer
Positive ions
gold
cations
Atoms
Electrons
atoms
electronics
carbon tetrachloride
Carbon tetrachloride
Carbon Tetrachloride
electromagnetic absorption
Quantum theory
thermal energy
quantum theory
Wave functions
Thermal energy
Light absorption

Keywords

  • Density functional theory
  • Marcus theory
  • Photo-induced electron transfer

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Physics and Astronomy(all)

Cite this

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title = "Theoretical calculation of the photo-induced electron transfer rate between a gold atom and a gold cation solvated in CCl4",
abstract = "A theoretical calculation was performed to evaluate the photo-induced electron transfer (PIET) rate between a gold atom and a gold ion solvated in carbon tetrachloride (CCl4) in the framework of Marcus electron transfer (ET) theory, including both solvent reorganization effects and electronic wavefunction coupling between the ET diabatic states. A novel component of this work involves calculation of the electronic coupling strength using a recently developed constrained real-time time-dependent density-functional-theory (CRT-TDDFT) method. It is found that the PIET rate reaches its maximum value at the electronic resonance wavelength regardless of the inter-particle separation, suggesting a strong correlation between PIET and light absorption. In comparison with thermally activated electron transfer (TAET) at room temperature, light irradiation is demonstrated to be much more efficient than thermal fluctuations in promoting long-range ET, at least for the most common situations, when the light travelling substantially exceeds thermal energy. This work is the first step towards a quantum theory of plasmon enhanced electron transfer, and the theory can also be used to calculate electron transfer rates quite generally for condensed phase problems.",
keywords = "Density functional theory, Marcus theory, Photo-induced electron transfer",
author = "Hanning Chen and Ratner, {Mark A} and Schatz, {George C}",
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T1 - Theoretical calculation of the photo-induced electron transfer rate between a gold atom and a gold cation solvated in CCl4

AU - Chen, Hanning

AU - Ratner, Mark A

AU - Schatz, George C

PY - 2011/6/25

Y1 - 2011/6/25

N2 - A theoretical calculation was performed to evaluate the photo-induced electron transfer (PIET) rate between a gold atom and a gold ion solvated in carbon tetrachloride (CCl4) in the framework of Marcus electron transfer (ET) theory, including both solvent reorganization effects and electronic wavefunction coupling between the ET diabatic states. A novel component of this work involves calculation of the electronic coupling strength using a recently developed constrained real-time time-dependent density-functional-theory (CRT-TDDFT) method. It is found that the PIET rate reaches its maximum value at the electronic resonance wavelength regardless of the inter-particle separation, suggesting a strong correlation between PIET and light absorption. In comparison with thermally activated electron transfer (TAET) at room temperature, light irradiation is demonstrated to be much more efficient than thermal fluctuations in promoting long-range ET, at least for the most common situations, when the light travelling substantially exceeds thermal energy. This work is the first step towards a quantum theory of plasmon enhanced electron transfer, and the theory can also be used to calculate electron transfer rates quite generally for condensed phase problems.

AB - A theoretical calculation was performed to evaluate the photo-induced electron transfer (PIET) rate between a gold atom and a gold ion solvated in carbon tetrachloride (CCl4) in the framework of Marcus electron transfer (ET) theory, including both solvent reorganization effects and electronic wavefunction coupling between the ET diabatic states. A novel component of this work involves calculation of the electronic coupling strength using a recently developed constrained real-time time-dependent density-functional-theory (CRT-TDDFT) method. It is found that the PIET rate reaches its maximum value at the electronic resonance wavelength regardless of the inter-particle separation, suggesting a strong correlation between PIET and light absorption. In comparison with thermally activated electron transfer (TAET) at room temperature, light irradiation is demonstrated to be much more efficient than thermal fluctuations in promoting long-range ET, at least for the most common situations, when the light travelling substantially exceeds thermal energy. This work is the first step towards a quantum theory of plasmon enhanced electron transfer, and the theory can also be used to calculate electron transfer rates quite generally for condensed phase problems.

KW - Density functional theory

KW - Marcus theory

KW - Photo-induced electron transfer

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