Time-Resolved X-ray Spectroscopy in the Water Window: Elucidating Transient Valence Charge Distributions in an Aqueous Fe(II) Complex

Benjamin E. Van Kuiken, Hana Cho, Kiryong Hong, Munira Khalil, Robert W. Schoenlein, Tae Kyu Kim, Nils Huse

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

Time-resolved nitrogen-1s spectroscopy in the X-ray water window is presented as a novel probe of metal-ligand interactions and transient states in nitrogen-containing organic compounds. New information on iron(II) polypyridyl complexes via nitrogen core-level transitions yields insight into the charge density of the photoinduced high-spin state by comparing experimental results with time-dependent density functional theory. In the transient high-spin state, the 3d electrons of the metal center are more delocalized over the nearest-neighbor nitrogen atoms despite increased bond lengths. Our findings point to a strong coupling of electronic states with charge-transfer character, facilitating the ultrafast intersystem crossing cascade in these systems. The study also highlights the importance of local charge density measures to complement chemical interaction concepts of charge donation and back-bonding with molecular orbital descriptions of states.

Original languageEnglish
Pages (from-to)465-470
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume7
Issue number3
DOIs
Publication statusPublished - 2016 Feb 4

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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