Optical spectra of transition-metal carbonyls: chromium hexacarbonyl, iron pentacarbonyl, and nickel tetracarbonyl

Kotzian, Manfred; Roesch, Notker; Schroeder, Hartmut; Zerner, Michael C.

doi:10.1021/ja00202a004

Cited by 147 publications

(97 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Experimentally, the spectrum of Ni(CO) 4 has been measured in solution, 84 in a matrix, 85 and recently in the gas phase. 86 did not go beyond this energy value) and are gathered in the upper part of Table 4 where the most reliable ab initio calculations have also been given, including the present TDDFT results at the BP/ALDA level. The excitation energies in Table 4 are the lowest dipole-allowed T 2 …”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

et al. 1999

View full text Add to dashboard Cite

The first time-dependent density functional theory (TDDFT) calculations on the spectra of molecules containing transition metals are reported. Three prototype systems are considered, of which the assignments are controversial: MnO 4 -, Ni(CO) 4 , and Mn 2 (CO) 10 . The TDDFT results are shown to be comparable in accuracy to the most elaborate ab initio calculations and lead to new insights in the spectra of these molecules. In some cases, the presented TDDFT results differ substantially, in both the ordering and the values for the excitation energies, from the older DFT method for the calculation of excitation energies: the ∆SCF approach. For the Mn 2 (CO) 10 molecule, the presented results are the highest-level theoretical results published so far. Over all, the results show that TDDFT can be a very useful tool in the calculation and interpretation of the spectra of transition metal compounds.

show abstract

Section: Resultsmentioning

confidence: 99%

“…In contrast to this, INDO/S CI 86 yields six of such states, CASSCF 69 yields zero (! ), and SECI yields two.…”

Section: Excitation Energies Of This Molecule Which Has T D Symmetrymentioning

confidence: 96%

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

et al. 1999

View full text Add to dashboard Cite

show abstract

“…The onset of the optical absorption spectrum is at 3.5 eV 17,18 . The optical absorption cross section is dominated by transitions from orbitals of predominantly Fe 3d character to orbitals with significant CO 2π character, i.e., metal-to-ligand charge transfer (MLCT) excitations 18–20 . Absorption of a photon with 4.66 eV energy (266 nm) by Fe(CO) 5 is followed by a primary dissociation step which splits off one CO, 21–23 creating the Fe(CO) 4 photofragment with a quantum yield close to unity 24 .…”

Section: Introductionmentioning

confidence: 99%

Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH

Kunnus

Josefsson

Rajković

et al. 2016

Structural Dynamics

View full text Add to dashboard Cite

We utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO)5 in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO)4 which are observed following a charge transfer photoexcitation of Fe(CO)5 as reported in our previous study [Wernet et al., Nature 520, 78 (2015)]. We find that branching of the reaction pathway likely happens in the 1A1 state of Fe(CO)4. A sub-picosecond time constant of the spin crossover from 1B2 to 3B2 is rationalized by the proposed 1B2 → 1A1 → 3B2 mechanism. Ultrafast ligation of the 1B2 Fe(CO)4 state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the 3B2 Fe(CO)4 ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via 1B2 → 1A1 → 1A′ Fe(CO)4EtOH pathway and the time scale of the 1A1 Fe(CO)4 state ligation is governed by the solute-solvent collision frequency. Our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.

show abstract

“…A high density of states, of often different chemical character in a narrow energy range, gives rise to broad-featureless experimental spectra [1,2]. We have previously shown how the supposedly simple TiO 2 molecule is challenging to describe [3].…”

Section: Introductionmentioning

confidence: 99%

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

Almeida¹,

McKinlay²,

Paterson³

2015

Chemical Physics

View full text Add to dashboard Cite

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.

show abstract

Optical spectra of transition-metal carbonyls: chromium hexacarbonyl, iron pentacarbonyl, and nickel tetracarbonyl

Cited by 147 publications

References 2 publications

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH

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

Contact Info

Product

Resources

About

Optical spectra of transition-metal carbonyls: chromium hexacarbonyl, iron pentacarbonyl, and nickel tetracarbonyl

Cited by 147 publications

References 2 publications

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO4-, Ni(CO)4, and Mn2(CO)10

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO4-, Ni(CO)4, and Mn2(CO)10

Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO)5 to Fe(CO)4EtOH

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

Contact Info

Product

Resources

About

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀