Transition Metals in Photocatalysis

Hennig, H.

doi:10.1002/9783527619399.ch6c

Cited by 4 publications

(1 citation statement)

References 21 publications

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“…Due to these properties, various classes of TMCs are actively employed, or show high potential, for a large number of innovative technological applications [1]. They are used in devices which convert solar energy, either directly to electrical current in dye-sensitized solar cells [2][3][4][5], to chemical energy of fuels in arti cial photosynthesis [6,7], or to complex chemicals in TMC-based photocatalysis [8][9][10]. Furthermore, TMCs are useful in photodynamic therapy [11][12][13], where light activates therapeutically bene cial chemical reactions that initiate apoptosis.…”

Section: Introductionmentioning

confidence: 99%

Quantitative wave function analysis for excited states of transition metal complexes

Mai

Dorn

Fumanal

et al. 2018

Coordination Chemistry Reviews

134

163

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The character of an electronically excited state is one of the most important descriptors employed to discuss the photophysics and photochemistry of transition metal complexes. In transition metal complexes, the interaction between the metal and the di erent ligands gives rise to a rich variety of excited states, including metal-centered, intra-ligand, metal-to-ligand charge transfer, ligand-to-metal charge transfer, and ligand-to-ligand charge transfer states. Most often, these excited states are identi ed by considering the most important wave function excitation coe cients and inspecting visually the involved orbitals. This procedure is tedious, subjective, and imprecise. Instead, automatic and quantitative techniques for excited-state characterization are desirable. In this contribution we review the concept of charge transfer numbers-as implemented in the TheoDORE package-and show its wide applicability to characterize the excited states of transition metal complexes. Charge transfer numbers are a formal way to analyze an excited state in terms of electron transitions between groups of atoms based only on the well-de ned transition density matrix. Its advantages are many: it can be fully automatized for many excited states, is objective and reproducible, and provides quantitative data useful for the discussion of trends or patterns. We also introduce a formalism for spin-orbit-mixed states and a method for statistical analysis of charge transfer numbers. The potential of this technique is demonstrated for a number of prototypical transition metal complexes containing Ir, Ru, and Re. Topics discussed include orbital delocalization between metal and carbonyl ligands, nonradiative decay through metal-centered states, e ect of spin-orbit couplings on state character, and comparison among results obtained from di erent electronic structure methods.

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