Electroabsorption studies of intervalence charge transfer in (NC)5FeCNOs(NH3)5: Experimental assessment of charge-transfer distance, solvent reorganization, and electronic coupling parameters

Laba Karki, Hong Peter Lu, Joseph T Hupp

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Abstract

Electroabsorption studies of (NC)5FeCNOs(NH3)5- show that light-induced metal-to-metal charge transfer is accompanied by a dipole moment change of -12.5 ± 1.5 D along the charge-transfer axis. This change corresponds to an effective one-electron transfer distance of 2.5 ± 0.3 A, i.e., less than half the geometric distance from iron to osmium. The charge-transfer distance revision has profound effects upon estimates for solvent reorganization and nonadiabatic electronic coupling energies. The distance revision decreases the former from 7000 to 2200 cm-1 and increases the latter from 1260 to 2600 cm-1. Reliable estimates for both, of course, are required in order to understand light-induced electron-transfer kinetics.

Original languageEnglish
Pages (from-to)15637-15639
Number of pages3
JournalJournal of Physical Chemistry
Volume100
Issue number39
Publication statusPublished - 1996

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Charge transfer
charge transfer
Metals
electronics
Osmium
electron transfer
Electrons
Dipole moment
osmium
estimates
Iron
metals
dipole moments
Kinetics
iron
kinetics
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Electroabsorption studies of intervalence charge transfer in (NC)5FeCNOs(NH3)5: Experimental assessment of charge-transfer distance, solvent reorganization, and electronic coupling parameters",
abstract = "Electroabsorption studies of (NC)5FeCNOs(NH3)5- show that light-induced metal-to-metal charge transfer is accompanied by a dipole moment change of -12.5 ± 1.5 D along the charge-transfer axis. This change corresponds to an effective one-electron transfer distance of 2.5 ± 0.3 A, i.e., less than half the geometric distance from iron to osmium. The charge-transfer distance revision has profound effects upon estimates for solvent reorganization and nonadiabatic electronic coupling energies. The distance revision decreases the former from 7000 to 2200 cm-1 and increases the latter from 1260 to 2600 cm-1. Reliable estimates for both, of course, are required in order to understand light-induced electron-transfer kinetics.",
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T1 - Electroabsorption studies of intervalence charge transfer in (NC)5FeCNOs(NH3)5

T2 - Experimental assessment of charge-transfer distance, solvent reorganization, and electronic coupling parameters

AU - Karki, Laba

AU - Lu, Hong Peter

AU - Hupp, Joseph T

PY - 1996

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N2 - Electroabsorption studies of (NC)5FeCNOs(NH3)5- show that light-induced metal-to-metal charge transfer is accompanied by a dipole moment change of -12.5 ± 1.5 D along the charge-transfer axis. This change corresponds to an effective one-electron transfer distance of 2.5 ± 0.3 A, i.e., less than half the geometric distance from iron to osmium. The charge-transfer distance revision has profound effects upon estimates for solvent reorganization and nonadiabatic electronic coupling energies. The distance revision decreases the former from 7000 to 2200 cm-1 and increases the latter from 1260 to 2600 cm-1. Reliable estimates for both, of course, are required in order to understand light-induced electron-transfer kinetics.

AB - Electroabsorption studies of (NC)5FeCNOs(NH3)5- show that light-induced metal-to-metal charge transfer is accompanied by a dipole moment change of -12.5 ± 1.5 D along the charge-transfer axis. This change corresponds to an effective one-electron transfer distance of 2.5 ± 0.3 A, i.e., less than half the geometric distance from iron to osmium. The charge-transfer distance revision has profound effects upon estimates for solvent reorganization and nonadiabatic electronic coupling energies. The distance revision decreases the former from 7000 to 2200 cm-1 and increases the latter from 1260 to 2600 cm-1. Reliable estimates for both, of course, are required in order to understand light-induced electron-transfer kinetics.

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