Time Dependent DFT Studies of Metal Core Electron Excitations in Mn Complexes

Date

2008

Authors

Jaszewski, Adrian
Stranger, Robert
Pace, Ronald

Journal Title

Journal ISSN

Volume Title

Publisher

American Chemical Society

Abstract

Time-dependent density functional theory (TDDFT) has been applied to study core excitations from Is and 2p Mn orbitais in a series of manganese complexes with oxygen and nitrogen donor ligands. The effect of basis set and functional on the excitation energy was evaluated in detail for one complex, Mn(acac) 2·(H2O)2. The results obtained for a range of compounds, namely, [Mn(Im)6]Cl2, Mn(CHsCOO) 2· 4H2O, Mn(acac)3, Mn(SALADHP) 2 and [Mn(SALPN)O]2, show good consistency with the data from X-ray absorption spectroscopy (XAS), confirming the relation between the Mn K-edge energy and the oxidation state of the Mn atom. The energies predicted for 2p core excitations show a dependence on the metal oxidation state very similar to that determined experimentally by ls2p resonant inelastic X-ray scattering (RIXS) studies for Mn(acac)2·(H2O) 2, Mn(acac)3, and Mn(sal)2(bipy). The reliability of the K-edge energies obtained in the present study indicates that TDDFT can be used in determining the oxidation states of Mn atoms in different computational models of the manganese cluster of photosystem II (PSII).

Description

Keywords

Keywords: Absorption spectroscopy; Atomic physics; Atomic spectroscopy; Atoms; Chemical oxygen demand; Density functional theory; Electron energy loss spectroscopy; Manganese; Manganese alloys; Oxidation; Oxygen; X ray scattering; X ray spectroscopy; Basis sets; Co

Citation

Source

Journal of Physical Chemistry A

Type

Journal article

Book Title

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DOI

10.1021/jp803286c

Restricted until

2037-12-31