344 research outputs found
Quantitative wave function analysis for excited states of transition metal complexes
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 different 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 identified by considering the most
important wave function excitation coefficients 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-defined 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, effect of spin-orbit couplings on state character, and
comparison among results obtained from different electronic structure methods.Comment: 47 pages, 19 figures, including supporting information (7 pages, 1
figure
Interstate Vibronic Coupling Constants Between Electronic Excited States for Complex Molecules
In the construction of diabatic vibronic Hamiltonians for quantum dynamics in
the excited-state manifold of molecules, the coupling constants are often
extracted solely from information on the excited-state energies. Here, a new
protocol is applied to get access to the interstate vibronic coupling constants
at the time-dependent density functional theory level through the overlap
integrals between excited-state adiabatic auxiliary wavefunctions. We discuss
the advantages of such method and its potential for future applications to
address complex systems, in particular those where multiple electronic states
are energetically closely lying and interact. As examples, we apply the
protocol to the study of prototype rhenium carbonyl complexes
[Re(CO)(N,N)(L)] for which non-adiabatic quantum dynamics within the
linear vibronic coupling model and including spin-orbit coupling have been
reported recently.Comment: 36 pages, 7 figures, 4 table
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