Ground and Excited State Properties and Vibronic Coupling Analysis of the Creutz−Taube Ion, [(NH3)5Ru-pyrazine-Ru(NH3)5]5+, Using DFT

Bencini, Alessandro; Ciofini, Ilaria; Daul, and Claude A.; Ferretti, Alessandro

doi:10.1021/ja9920258

Cited by 88 publications

(91 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Compound [3] 5+ has probably been investigated more extensively than any other MV complex, through detailed experimental measurements in the solid state [56][57][58] and in solution, [26,59,60] and also using quantum-chemical methods. [61][62][63][64][65][66] The UV-vis-NIR spectrum of [3] 5+ exhibits a single asymmetric band envelope with no notable shoulders (preventing simple Gaussian fitting). The asymmetric band shape can be explained by vibronic coupling, [1,13] which is not considered here.…”

Section: The Minima Deloc-[2-me]mentioning

confidence: 99%

Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

Parthey

Gluyas

Fox

et al. 2014

Chemistry A European J

107

View full text Add to dashboard Cite

Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

show abstract

Section: The Minima Deloc-[2-me]mentioning

confidence: 99%

Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

Parthey

Gluyas

Fox

et al. 2014

Chemistry A European J

107

View full text Add to dashboard Cite

show abstract

“…The h DA d (2) values obtained in the present work with both optimized and adjusted geometries lie within the upper and lower bounds for H DA d (2) suggested by Reimers and Hush (∼ 2400-3600 cm -1 ). 78 The geometry (especially r RuN(pz) ) is, in turn, found to be sensitive to the basis set employed 77 and is also likely to depend on the environment of the complex (e.g., in vacuo, aqueous solution, or crystalline solid). 78 Strictly speaking, H DA d (2) should be less than one-half the vertical gap, ∆E 12 a(2) (eq 10) by a term depending on the reorganization energy due to symmetric normal modes of the solute, a correction likely to be a few hundred cm -1 .…”

Section: Projection Analysis Of ψ D D(n) and ψ A D(n)mentioning

confidence: 99%

Reduced Electronic Spaces for Modeling Donor/Acceptor Interactions

et al. 2010

View full text Add to dashboard Cite

Diabatic states for donor (D) and acceptor (A) interactions in electron transfer (ET) processes are formulated and evaluated, along with coupling elements (H DA ) and effective D/A separation distances (r DA ), for reduced electronic spaces of variable size, using the generalized Mulliken Hush model (GMH), applicable to an arbitrary state space and nuclear configuration, and encompassing Robin-Day class III and as well as class II situations. Once the electronic state space is selected (a set of n g 2 adiabatic states approximated by an orbital space based on an effective 1-electron (1-e) Hamiltonian), the charge-localized GMH diabatic states are obtained as the eigenstates of the dipole moment operator, with rotations to yield locally adiabatic states for sites with multiple states. The 1-e states and energies are expressed in terms of Kohn-Sham orbitals and orbital energies. Addressing questions as to whether the estimate of H DA "improves" as one increases n, and in what sense the GMH approach "converges" with n, we carry out calculations for three mixed-valence binuclear Ru complexes, from which we conclude that the 2-state (2-st) model gives the most appropriate estimate of the effectiVe coupling, similar (to within a rms deviation of e15%) to coupling elements obtained by superexchange correction of H DA values based on larger spaces (n ) 3-6), and thus yielding a quasi-invariant value for H DA over the range explored in the calculations (n ) 2-6). An analysis of the coupling and associated D and A states shows that the 2-st coupling involves crucial mixing with intervening bridge states (D and A "tails"), while increasingly larger state spaces for the same system yield increasingly more localized D and A states (and weaker coupling), with H DA tending to approach the limit of "bare" or "through space" coupling. These results help to reconcile seemingly contradictory assertions in the recent literature regarding the proper role of multistate frameworks in the formulation of coupling for both intra-and intermolecular ET systems.The present results are compared in detail with other reported results.

show abstract

“…Density functional theory (DFT) has been applied to the electronic and molecular structure of [(NH 3 ) 5 Ru(pz)Ru(NH 3 ) 5 ] 5C assuming delocalization (Bencini et al 1999). Energy minimization based on INDO/1 calculations predicts an unsymmetrical structure (Broo & Lincoln 1997).…”

Section: Introductionmentioning

confidence: 99%

Probing the localized-to-delocalized transition

Concepcion

Dattelbaum

Meyer

et al. 2007

Phil. Trans. R. Soc. A.

View full text Add to dashboard Cite

Detailed understanding of the transition between localized and delocalized behaviour in mixed valence compounds has been elusive as evidenced by many interpretations of the Creutz-Taube ion, [(NH 3 ) 5 Ru(pz)Ru(NH 3 ) 5 ] 5C . In a review in 2001, experimental protocols and a systematic model to probe this region were proposed and applied to examples in the literature. The model included: (i) multiple orbital interactions in ligand-bridged transition metal complexes, (ii) inclusion of spin-orbit coupling which, for dp 5 -dp 6 complexes, leads to five low-energy bands, two from interconfigurational (dp/dp) transitions at the dp 5 site and three from intervalence transfer transitions, (iii) differences in time scale between coupled vibrations and solvent modes which can result in solvent averaging with continued electronic asymmetry defining 'class II-III', an addition to the Robin-Day classification scheme, and (iv) delineation of coupled vibrations into barrier vibrations and 'spectator' vibrations. The latter provide direct insight into localization or delocalization and time scales for electron transfer. In this paper, the earlier model is applied to a series of mixed-valence molecules.

show abstract

Ground and Excited State Properties and Vibronic Coupling Analysis of the Creutz−Taube Ion, [(NH₃)₅Ru-pyrazine-Ru(NH₃)₅]⁵⁺, Using DFT

Cited by 88 publications

References 49 publications

Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

Reduced Electronic Spaces for Modeling Donor/Acceptor Interactions

Probing the localized-to-delocalized transition

Contact Info

Product

Resources

About