title: Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory.
abstract: Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a powerful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with conventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We consider seven low- and high-spin model complexes involving chromium, manganese, and iron transition metal centers. Our results are in good agreement with experiment.
authors.affiliation: Department of Chemistry, University of California , Irvine, California 92697, United States.
authors.forename: Yu
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, University of California , Irvine, California 92697, United States.
authors.forename: Shaul
authors.initials: S
authors.lastname: Mukamel
authors.affiliation: Department of Chemistry, University of Washington , Seattle, Washington 98195, United States.
authors.forename: Munira
authors.initials: M
authors.lastname: Khalil
authors.affiliation: Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.
authors.forename: Niranjan
authors.initials: N
authors.lastname: Govind