How fast is optically induced electron transfer in organic mixed valence systems?

被引：14

作者：

Lambert, C. ^{[1
]}

Moos, M. ^{[1
]}

Schmiedel, A. ^{[1
]}

Holzapfel, M. ^{[1
]}

Schaefer, J. ^{[1
]}

Kess, M. ^{[2
]}

Engel, V. ^{[2
]}

机构：

[1] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany

[2] Univ Wurzburg, Inst Phys & Theoret Chem, Emil Fischer Str 42, D-97074 Wurzburg, Germany

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2016年 / 18卷 / 28期

关键词：

TRANSIENT ABSORPTION-SPECTROSCOPY; VIBRATIONAL-ENERGY RELAXATION; PUMP-PROBE SPECTROSCOPY; CHARGE-TRANSFER; EXCITED-STATE; MULLIKEN-HUSH; SCHRODINGER-EQUATION; INTERNAL-CONVERSION; SOLVATION DYNAMICS; RAMAN-SPECTROSCOPY;

D O I：

10.1039/c6cp03053j

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The rate of thermally induced electron transfer in organic mixed valence compounds has thoroughly been investigated by e.g. temperature dependent ESR spectroscopy. However, almost nothing is known about the dynamics of optically induced electron transfer processes in such systems. Therefore, we investigated these processes in mixed valence compounds based on triphenylamine redox centres bridged by conjugated spacers by NIR transient absorption spectroscopy with fs-time resolution. These experiments revealed an internal conversion (IC) process to be on the order of 50-200 fs which is equivalent to the back electron transfer after optical excitation into the intervalence charge transfer band. This IC is followed by ultrafast cooling to the ground state within 1 ps. Thus, in the systems investigated optically induced electron transfer is about 3-4 orders of magnitude faster than thermally induced ET.

引用

页码：19405 / 19411

页数：7

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