Advanced aspects of ab initio theoretical optical spectroscopy of transition metal complexes: Multiplets, spin-orbit coupling and resonance Raman intensities

Neese, Frank; Petrenko, Taras; Ganyushin, Dmitry; Olbrich, G.

doi:10.1016/j.ccr.2006.05.019

Cited by 299 publications

(327 citation statements)

References 246 publications

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“…Quantum chemical calculations of excited states also often neglect SOC. Nevertheless, spin-free CASSCF/CASPT2-type [5][6][7][8] and (TD)DFT [8][9][10] techniques are still instrumental in interpreting photophysical behavior and spectra. DFT techniques with hybrid functionals are successfully used to visualize singlet and triplet CT states and reveal their characters by displaying differences of electron density distribution upon excitation and/or excited-state spin-density distributions [9][10][11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Relativistic effects in spectroscopy and photophysics of heavy-metal complexes illustrated by spin–orbit calculations of [Re(imidazole)(CO)3(phen)]+

Baková

Chergui

Daniel

et al. 2011

Coordination Chemistry Reviews

111

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Section: Introductionmentioning

confidence: 99%

Relativistic effects in spectroscopy and photophysics of heavy-metal complexes illustrated by spin–orbit calculations of [Re(imidazole)(CO)3(phen)]+

Baková

Chergui

Daniel

et al. 2011

Coordination Chemistry Reviews

111

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“…Following the same ideas, Malrieu and co-workers 15,16 developed the difference dedicated configuration interaction ͑DDCI͒ approach where the CI matrix only contains those configurations playing a role on the energy difference of the states involved in the coupling. Based on the same idea, Neese and co-workers 17,18 recently developed and coded the spectroscopy oriented CI method focused to the study of transition metal complexes. Recently, Barone et al 19 also coded a modified DDCI2 version of the method and applied to organic biradicals.…”

Section: Introductionmentioning

confidence: 99%

Analysis of the magnetic coupling in binuclear systems. III. The role of the ligand to metal charge transfer excitations revisited

Calzado

Angeli

Taratiel

et al. 2009

The Journal of Chemical Physics

119

179

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In magnetic coordination compounds and solids the magnetic orbitals are essentially located on metallic centers but present some delocalization tails on adjacent ligands. Mean field variational calculations optimize this mixing and validate a single band modelization of the intersite magnetic exchange. In this approach, due to the Brillouin's theorem, the ligand to metal charge transfer ͑LMCT͒ excitations play a minor role. On the other hand the extensive configuration interaction calculations show that the determinants obtained by a single excitation on the top of the LMCT configurations bring an important antiferromagnetic contribution to the magnetic coupling. Perturbative and truncated variational calculations show that contrary to the interpretation given in a previous article ͓C. J. Calzado et al., J. Chem. Phys. 116, 2728 ͑2002͔͒ the contribution of these determinants to the magnetic coupling constant is not a second-order one. An analytic development enables one to establish that they contribute at higher order as a correlation induced increase in the LMCT components of the wave function, i.e., of the mixing between the ligand and the magnetic orbitals. This larger delocalization of the magnetic orbitals results in an increase in both the ferroand antiferromagnetic contributions to the coupling constant.

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“…Often, the short-time approximation to propagation dynamics is introduced, 27 which has proven remarkably useful in interpreting resonance Raman spectra. [27][28][29] Finally, resonance Raman cross section can be expressed in a fashion analogous to the nonresonant case by introducing finite lifetimes for the intermediate states, or in other words, by computing Raman cross sections from derivatives of electronic polarizabilities evaluated at complex frequenciesω = ω + iγ. 30,31 Here ω is the excitation frequency and γ corresponds to an averaged lifetime of excited states, which is usually treated as an empirical parameter.…”

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confidence: 99%

Simplified Sum-Over-States Approach for Predicting Resonance Raman Spectra. Application to Nucleic Acid Bases

Rappoport

Shim

Aspuru‐Guzik

2011

J. Phys. Chem. Lett.

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Resonance Raman spectra provide a valuable probe into molecular excited-state structures and properties. Moreover, resonance enhancement is of importance for the chemical contribution to surface-enhanced Raman scattering. In this work, we introduce a simplified sum-over-states scheme for computing Raman spectra and Raman excitation profiles. The proposed sum-over-states approach uses derivatives of electronic excitation energies and transition dipole moments, which can be efficiently computed from time-dependent density functional theory. We analyze and interpret the resonance Raman spectra and Raman excitation profiles of nucleic acid bases using the present approach. Contributions of individual excited states under strictly resonant and nonresonant conditions are investigated, and smooth interpolation between both limiting cases is obtained.

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Advanced aspects of ab initio theoretical optical spectroscopy of transition metal complexes: Multiplets, spin-orbit coupling and resonance Raman intensities

Cited by 299 publications

References 246 publications

Relativistic effects in spectroscopy and photophysics of heavy-metal complexes illustrated by spin–orbit calculations of [Re(imidazole)(CO)3(phen)]+

Relativistic effects in spectroscopy and photophysics of heavy-metal complexes illustrated by spin–orbit calculations of [Re(imidazole)(CO)3(phen)]+

Analysis of the magnetic coupling in binuclear systems. III. The role of the ligand to metal charge transfer excitations revisited

Simplified Sum-Over-States Approach for Predicting Resonance Raman Spectra. Application to Nucleic Acid Bases

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