Computation of Excited States of Transition Metal Complexes

Almeida, Nuno Miguel da Silva; McKinlay, Russell G.; Paterson, Martin J.

doi:10.1007/430_2014_151

Cited by 10 publications

(10 citation statements)

References 76 publications

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“…That the accurate computational description of excited states of TMCs is a formidable challenge is evidenced by the large amount of literature devoted to this topic, see, e.g., Refs [1,[25][26][27][39][40][41][42][43][44][45][46][47]. The di erent classes of excited states depend to a di erent extent on the description of electronic correlation and exchange e ects, necessitating a well-balanced method.…”

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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“…Unlike correlated wavefunction methods TD-DFT has been extensively applied to this system so we will limit our discussion here to more recent results. Van Gisbergen et al performed an extensive study comparing different TD-DFT methods in transition metals for MnO 4 À , Ni(CO) 4 and Mn 2 (CO) 10 [29]. They obtained the first four 1 T 2 excited states at 2.82 eV, 3.89 eV, 4.74 eV and 5.84 eV using the BP functional, and 2.63 eV, 3.60 eV, 4.52 eV and 5.46 eV for LB94.…”

Section: Td-dft Resultsmentioning

confidence: 99%

“…However, for certain inorganic molecules we have shown that the same levels of accuracy may not be obtained and the nature of the electron correlation in the ground (reference) state the Refs. [3,4].…”

Section: Mnomentioning

confidence: 98%

“…We have previously shown how the supposedly simple TiO 2 molecule is challenging to describe [3]. The challenges when trying to accurately study the electronic excited states of transition metal complexes present a hurdle on the path to fully understanding the rich and varied reactive photochemistry that many transition metal complexes display, with more cases being reported regularly, see for example [4][5][6][7][8][9][10][11]. There are also a number of wellknown complexes that despite their modest size and simple structure have been classed as 'tough' examples when trying to fully understand the nature of their ground and electronic excited states due to often poor agreement between many theoretical methods and experiment [12].…”

Section: Introductionmentioning

confidence: 98%

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Excited electronic states of MnO4−: Challenges for wavefunction and density functional response theories

Almeida¹,

McKinlay²,

Paterson³

2015

Chemical Physics

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a b s t r a c tThe lowest excited electronic states of the permanganate ion MnO 4 À are calculated using a hierarchy of coupled cluster response approaches, as well as time-dependent density functional theory. It is shown that while full linear response coupled cluster with singles and doubles (or higher) performs well, that permanganate represents a stern test for approximate coupled cluster response models, and that problems can be traced to very large orbital relaxation effects. TD-DFT is reasonably robust although errors around 0.6 eV are still observed. In order to further investigate the strong correlations prevalent in the electronic ground state large-scale RASSCF calculations were also performed. Again very large orbital relaxation in the correlated wavefunction is observed. Although the system can qualitatively be described by a single configuration, multi-reference diagnostic values show that care must be taken in this and similar metal complexes.

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“…(i) At the higher-energy band (using the 295 nm light): It is well known that spin-allowed absorption cross-sections are basically larger than those for spin-forbidden excitations. [58][59][60][61][62][63] Moreover, as seen in the le-hand side of Fig. 2, once Mn-S 0 -Rea is absorbed by light with 295 nm, the possibility for the Mn complex relaxing from the singlet FC zone to the triplet region is quite slim, since the excited Mn complex would initially jump to the nearby singlet excited state.…”

Section: Resultsmentioning

confidence: 99%

The mechanistic investigations of photochemical carbonyl elimination and oxidative addition reactions of (η⁵-C₅H₅)M(CO)₃, (M = Mn and Re) complexes

2018

RSC Adv.

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Computation of Excited States of Transition Metal Complexes

Cited by 10 publications

References 76 publications

Quantitative wave function analysis for excited states of transition metal complexes

Quantitative wave function analysis for excited states of transition metal complexes

Excited electronic states of MnO4−: Challenges for wavefunction and density functional response theories

The mechanistic investigations of photochemical carbonyl elimination and oxidative addition reactions of (η⁵-C₅H₅)M(CO)₃, (M = Mn and Re) complexes

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Computation of Excited States of Transition Metal Complexes

Cited by 10 publications

References 76 publications

Quantitative wave function analysis for excited states of transition metal complexes

Quantitative wave function analysis for excited states of transition metal complexes

Excited electronic states of MnO4−: Challenges for wavefunction and density functional response theories

The mechanistic investigations of photochemical carbonyl elimination and oxidative addition reactions of (η5-C5H5)M(CO)3, (M = Mn and Re) complexes

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The mechanistic investigations of photochemical carbonyl elimination and oxidative addition reactions of (η⁵-C₅H₅)M(CO)₃, (M = Mn and Re) complexes