Charge-displacement analysis for excited states

Ronca, Enrico; Pastore, Mariachiara; Belpassi, Leonardo; Angelis, Filippo De; Angeli, Celestino; Cimiraglia, Renzo; Tarantelli, Francesco

doi:10.1063/1.4863411

Cited by 31 publications

(28 citation statements)

References 172 publications

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“…The factors above challenge the analysis of excited-state computations, so that in many cases quantitative or even qualitative insight from the computational results is di cult to obtain. In this direction, recent developments have been proposed-mostly focused on the DFT framework-for rationalizing and interpreting charge transfer excited-states properties [61][62][63][64][65][66][67][68][69]. These methods are very suitable for analyzing the strength of charge transfer of low lying states in molecular systems with a clear donor-acceptor structure.…”

Section: Introductionmentioning

confidence: 99%

Quantitative wave function analysis for excited states of transition metal complexes

Mai

Dorn

Fumanal

et al. 2018

Coordination Chemistry Reviews

130

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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Section: Introductionmentioning

confidence: 99%

Quantitative wave function analysis for excited states of transition metal complexes

Mai

Dorn

Fumanal

et al. 2018

Coordination Chemistry Reviews

130

163

View full text Add to dashboard Cite

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“…This provides specific information about the involvement of the different atoms with the downside of being dependent on the specific population analysis scheme chosen. Finally, a number of measures for quantifying charge transfer have been suggested . While these can provide specific information of interest, the interpretation of the results is hampered by the lack of a universal underlying physical picture.…”

Section: Introductionmentioning

confidence: 99%

Statistical analysis of electronic excitation processes: Spatial location, compactness, charge transfer, and electron-hole correlation

et al. 2015

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We report the development of a set of excited-state analysis tools that are based on the construction of an effective exciton wavefunction and its statistical analysis in terms of spatial multipole moments. This construction does not only enable the quantification of the spatial location and compactness of the individual hole and electron densities but also correlation phenomena can be analyzed, which makes this procedure particularly useful when excitonic or charge-resonance effects are of interest. The methods are first applied to bianthryl with a focus on elucidating charge-resonance interactions. It is shown how these derive from anticorrelations between the electron and hole quasiparticles, and it is discussed how the resulting variations in state characters affect the excited-state absorption spectrum. As a second example, cytosine is chosen. It is illustrated how the various descriptors vary for valence, Rydberg, and core-excited states, and the possibility of using this information for an automatic characterization of state characters is discussed.

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“…Chemical insights will be drawn about the nature of halogen bond, its cooperativity and its influence on metal-ligand bond components.Molecules 2020, 25, 300 2 of 17 Some years ago, the Charge Displacement (CD) function was introduced to study the chemical bond between noble metals and noble gases [13] and then applied to various kind of chemical interactions. These include the quantitative study of charge transfer in hydrogen bonding [14][15][16] and halogen bonding [17,18] in weakly bound adducts, to characterize charge transfer (CT) effects on conduction band of dye sensitized solar cells [19] and also to describe the charge rearrangement in the electronic excited states [20]. Above all, it provided to be extremely versatile in coordination chemistry.…”

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confidence: 99%

Charge Displacement Analysis—A Tool to Theoretically Characterize the Charge Transfer Contribution of Halogen Bonds

Ciancaleoni

Nunzi

Belpassi³

2020

Molecules

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Theoretical bonding analysis is of prime importance for the deep understanding of the various chemical interactions, covalent or not. Among the various methods that have been developed in the last decades, the analysis of the Charge Displacement function (CD) demonstrated to be useful to reveal the charge transfer effects in many contexts, from weak hydrogen bonds, to the characterization of σ hole interactions, as halogen, chalcogen and pnictogen bonding or even in the decomposition of the metal-ligand bond. Quite often, the CD analysis has also been coupled with experimental techniques, in order to give a complete description of the system under study. In this review, we focus on the use of CD analysis on halogen bonded systems, describing the most relevant literature examples about gas phase and condensed phase systems. Chemical insights will be drawn about the nature of halogen bond, its cooperativity and its influence on metal-ligand bond components.

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Charge-displacement analysis for excited states

Cited by 31 publications

References 172 publications

Quantitative wave function analysis for excited states of transition metal complexes

Quantitative wave function analysis for excited states of transition metal complexes

Statistical analysis of electronic excitation processes: Spatial location, compactness, charge transfer, and electron-hole correlation

Charge Displacement Analysis—A Tool to Theoretically Characterize the Charge Transfer Contribution of Halogen Bonds

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