skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: X-ray absorption structural study of a reversible, photoexcited charge-transfer state

Abstract

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.

Authors:
; ;  [1];  [2]
  1. Argonne National Lab., IL (United States) Univ. of Chicago, IL (United States)
  2. Argonne Nationa Lab., IL (United States)
Publication Date:
OSTI Identifier:
6043528
DOE Contract Number:  
W-31109-ENG-38
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (United States)
Additional Journal Information:
Journal Volume: 115:10; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, 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

Citation Formats

Chen, L X, Bowman, M K, Norris, J R, and Montano, P A. X-ray absorption structural study of a reversible, photoexcited charge-transfer state. United States: N. p., 1993. Web. doi:10.1021/ja00063a070.
Chen, L X, Bowman, M K, Norris, J R, & Montano, P A. X-ray absorption structural study of a reversible, photoexcited charge-transfer state. United States. https://doi.org/10.1021/ja00063a070
Chen, L X, Bowman, M K, Norris, J R, and Montano, P A. 1993. "X-ray absorption structural study of a reversible, photoexcited charge-transfer state". United States. https://doi.org/10.1021/ja00063a070.
@article{osti_6043528,
title = {X-ray absorption structural study of a reversible, photoexcited charge-transfer state},
author = {Chen, L X and Bowman, M K and Norris, J R and Montano, P A},
abstractNote = {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.},
doi = {10.1021/ja00063a070},
url = {https://www.osti.gov/biblio/6043528}, journal = {Journal of the American Chemical Society; (United States)},
issn = {0002-7863},
number = ,
volume = 115:10,
place = {United States},
year = {Wed May 19 00:00:00 EDT 1993},
month = {Wed May 19 00:00:00 EDT 1993}
}