X-ray absorption structural study of a reversible, photoexcited charge-transfer state
- Argonne National Lab., IL (United States) Univ. of Chicago, IL (United States)
- Argonne Nationa Lab., IL (United States)
Electron-transfer reactions can be accompanied by significant nuclear movements. Nuclear motion appears to be especially vital to the reversible, photoinduced charge-transfer chemistry of cyclopentadienylnickel nitrosyl (C[sub 5]H[sub 5]NiNO). Although extended X-ray absorption fine structure (EXAFS) spectroscopy has recorded photoinduced changes in the ligation of myoglobins, similar X-ray studies of electron-transfer chemistry have not been reported. Here we examine reversible, photoinduced structural changes in C[sub 5]H[sub 5]NiNO by EXAFS and propose a mechanism for the electron-transfer chemistry. This work demonstrates that EXAFS can measure distance changes accompanying photoinduced electron transfer to provide new details of the geometry of photoexcited state and suggests that electron transfer occurs in the transient, optically excited states of C[sub 5]H[sub 5]NiNO and C[sub 5]H[sub 5]NiNO[sup CT] as dictated by NO movement that produces either C[sub 5]H[sub 5]NiNO[sup CT] or C[sub 5]H[sub 5]NiNO[sup GS]. 14 refs., 2 figs.
- DOE Contract Number:
- W-31109-ENG-38
- OSTI ID:
- 6043528
- Journal Information:
- Journal of the American Chemical Society; (United States), Vol. 115:10; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
Similar Records
EXAFS studies on the structure of photoexcited cyclopentadienylnickelnitrosyl(C[sub 5]H[sub 5]NiNO)
Structural studies of photoinduced intramolecular electron transfer in cyclopentadienylnickelnitrosyl
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
NICKEL COMPLEXES
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
X-RAY SPECTROSCOPY
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMISTRY
CHEMISTRY
COMPLEXES
ORGANIC COMPOUNDS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400500* - Photochemistry
400102 - Chemical & Spectral Procedures