Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes: Deciphering the Interplay of Electronic and Structural Dynamics

Nils Huse; Hana Cho; Kiryong Hong; Lindsey Jamula; Frank M F de Groot; Tae Kyu Kim; James K McCusker; Robert W Schoenlein

doi:10.1021/jz200168m

Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes: Deciphering the Interplay of Electronic and Structural Dynamics

J Phys Chem Lett. 2011 Apr 21;2(8):880-4. doi: 10.1021/jz200168m. Epub 2011 Mar 30.

Authors

Nils Huse¹, Hana Cho^{1

2}, Kiryong Hong², Lindsey Jamula³, Frank M F de Groot⁴, Tae Kyu Kim², James K McCusker³, Robert W Schoenlein¹

Affiliations

¹ †Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
² ‡Department of Chemistry and Chemistry Institute of Functional Materials, Pusan National University, Busan 609-735, Republic of Korea.
³ §Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, United States.
⁴ ⊥Department of Chemistry, Utrecht University, 3584 Utrecht, Netherlands.

PMID: 26295622
DOI: 10.1021/jz200168m

Abstract

We present the first implementation of femtosecond soft X-ray spectroscopy as an ultrafast direct probe of the excited-state valence orbitals in solution-phase molecules. This method is applied to photoinduced spin crossover of [Fe(tren(py)3)](2+), where the ultrafast spin-state conversion of the metal ion, initiated by metal-to-ligand charge-transfer excitation, is directly measured using the intrinsic spin-state selectivity of the soft X-ray L-edge transitions. Our results provide important experimental data concerning the mechanism of ultrafast spin-state conversion and subsequent electronic and structural dynamics, highlighting the potential of this technique to study ultrafast phenomena in the solution phase.

Keywords: X-ray absorption spectroscopy; charge transfer; femtochemistry; spin crossover; structural dynamics; transition metals.