Absorption Spectra of Several Metal Complexes Revisited by the Time-Dependent Density-Functional Theory-Response Theory Formalism

Boulet, Pascal; Chermette, Henry; Daul, Claude; Gilardoni, François; Rogemond, F.; Weber, Jacques; Zuber, Gérard

doi:10.1021/jp003041q

Cited by 97 publications

(80 citation statements)

References 49 publications

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“…6,10,12,15 Excited state number 2 at 2.24 eV seems to be responsible for the shoulder at 2.35 eV, which was suggested by Scott and Becker 16 and by Scuppa et al 12 to arise from a triplet excitation. The assignment of excited state 2 to the 2.35 eV shoulder, however, is in agreement with the disappearance of this peak and the color change of ferrocene from orange to yellow upon cooling.…”

Section: Journal Of Chemical Theory and Computationmentioning

confidence: 80%

“…It is demonstrated that B3LYP works perfectly fine and that the differences between B3LYP results and experiment found in earlier studies arise from incorrect assignment of the excited states, 6,10,12,15 use of inadequate pseudopotentials, 6 and that agreement between theory and experiment at other levels of theory was manipulated by using Cp−Fe distances that were too short. 6,12 Based on ligand field theory, the low-energy peaks are assigned to be d−d transitions and the stronger absorptions to charge-transfer (CT) states. 15,21 Analysis of density differences and charge differences on Fe between ground and excited states reveals that low-and high-lying excited states involve similar amounts of charge transfer, so that the distinction between n d−d and CT transitions 21 is not justified.…”

Section: ■ Introductionmentioning

confidence: 84%

“…Table 2 summarizes relevant results from previous theoretical studies, leading to the conclusion that TDB3LYP should not be used to calculate the absorption spectrum of ferrocene. Boulet et al 6 employed timedependent density functional response theory (TDDFRT) with LDA and gradient corrected functionals. The basis sets consisted of pseudo-potentials plus Slater-type polarized triple-ζ valence basis sets.…”

Section: Journal Of Chemical Theory and Computationmentioning

confidence: 99%

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Quantitatively Correct UV-vis Spectrum of Ferrocene with TDB3LYP

Salzner

2013

J. Chem. Theory Comput.

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The ultraviolet−visible light (UV-vis) absorption spectrum of ferrocene is modeled with time-dependent density functional theory employing LSDA, BLYP, B3LYP, and CAM-B3LYP functionals in combination with 6-31G*, 6-31+G*, CC-PVTZ, and aug-CC-PVTZ basis sets. With the exception of LSDA, all functionals predict a reasonable Fe-CP distance of ∼1.67 Å. Diffuse functions are essential for the strongly allowed states at high energy but of lesser consequence for the visible range of the spectrum. Dipole forbidden states are examined with vibrationally excited structures, obtained from the normal modes of the infrared (IR) spectrum. Despite earlier claims, TDB3LYP predicts the UV−vis spectrum of ferrocene quantitatively correct. TDBLYP predicts a large number of spurious charge-transfer states, TDCAM-B3LYP and TDwB97XD are correct in the low-energy region but overestimate the energy of strongest peak of the spectrum by 0.8 eV. The amount of charge transfer involved in "d−d transitions" is equal to that in "charge-transfer states". ■ INTRODUCTIONFerrocene was discovered in 1951 1 and has revolutionized the views of chemists about how metals bind to organic π-systems. Its electronic structure and ultraviolet-visible light (UV-vis) absorption spectrum have become textbook 2 examples, and one would assume that not much new can be said about them. However, comparison between results obtained with timedependent density functional theory (TDDFT) by the author and theoretical data from the literature 3−15 revealed several discrepancies, which prompted the present investigation.Pure ferrocene is a very stable light orange powder, and the UV−vis absorption spectrum of ferrocene has been investigated in detail. 16−19 Upon cooling, the color changes from orange to lemon yellow. 16,17 The orange color stems from a dipoleforbidden absorption at 440 nm (2.81 eV) and a shoulder at 528 nm (2.34 eV), 16−18 both of which gain oscillator strength only through vibronic coupling. 8 Outside the visible range, a weak peak occurs at 324 nm (3.83 eV) and several relatively weak but allowed absorptions are present between 265 nm and 230 nm. The strongest absorption of ferrocene is observed at 202 nm (6.12 eV) in solution and 6.31 eV in the vapor phase. 16−19 The oscillator strength of this allowed absorption is 350 times stronger than that of the peak at 440 nm.B3LYP produces the structural parameters of ferrocene with errors of 2 pm or less, 20 and there is consensus that, in agreement with experiment, theory predicts the eclipsed form to be more stable than the staggered one. Several authors have cautioned, however, against using B3LYP for excited-state calculations of ferrocene. 6,10,12,15 Boulet et al., 6 Li et al., 10 and Scuppa et al. 12 promoted gradient-corrected pure DFT functionals, and Fromager et al. 15 promoted the rangeseparated CAM-B3LYP functional. In this investigation, TDDFT results with several functionals and different allelectron basis sets are analyzed. It is demonstrated that B3LYP works perfectly fine and that t...

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Section: Journal Of Chemical Theory and Computationmentioning

confidence: 80%

Section: ■ Introductionmentioning

confidence: 84%

Section: Journal Of Chemical Theory and Computationmentioning

confidence: 99%

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Quantitatively Correct UV-vis Spectrum of Ferrocene with TDB3LYP

Salzner

2013

J. Chem. Theory Comput.

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“…As an illustrative example we computed the lowlying singlet excitation spectrum of ferrocene for which experimental solution data [61,62] as well as ample theoretical ab initio gas-phase reference values [49,50,[63][64][65] are available.…”

Section: Ferrocenementioning

confidence: 99%

Multi-configuration time-dependent density-functional theory based on range separation

Fromager

Knecht²,

Jensen

2013

The Journal of Chemical Physics

162

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Multi-configuration range-separated density-functional theory is extended to the time-dependent regime. An exact variational formulation is derived. The approximation, which consists in combining a long-range Multi-Configuration-Self-Consistent Field (MCSCF) treatment with an adiabatic short-range density-functional (DFT) description, is then considered. The resulting time-dependent multi-configuration short-range DFT (TD-MC-srDFT) model is applied to the calculation of singlet excitation energies in H 2 , Be and ferrocene, considering both short-range local density (srLDA) and

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“…[44,45] As the calculations on excitedstate properties using post-Hartree-Fock methods require more computational effort, time-dependent density functional theory (TD-DFT) would be attractive in the present study due to its lower computational cost and more superior results than single-excitation configuration interaction (CIS) or time-dependent Hartree-Fock (TD-HF) in predicting the vertical electronic excitation spectra. [46][47][48] …”

Section: A C H T U N G T R E N N U N G [Nds*a C H T U N G T R E N N Umentioning

confidence: 99%

The ³[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

Tong

Kui

Chao

et al. 2009

Chemistry A European J

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The complexes [Au(3)(dcmp)(2)][X](3) {dcmp=bis(dicyclohexylphosphinomethyl)cyclohexylphosphine; X=Cl(-) (1), ClO(4) (-) (2), OTf(-) (3), PF(6) (-) (4), SCN(-)(5)}, [Ag(3)(dcmp)(2)][ClO(4)](3) (6), and [Ag(3)(dcmp)(2)Cl(2)][ClO(4)] (7) were prepared and their structures were determined by X-ray crystallography. Complexes 2-4 display a high-energy emission band with lambda(max) at 442-452 nm, whereas 1 and 5 display a low-energy emission with lambda(max) at 558-634 nm in both solid state and in dichloromethane at 298 K. The former is assigned to the (3)[5dsigma*6psigma] excited state of [Au(3)(dcmp)(2)](3+), whereas the latter is attributed to an exciplex formed between the (3)[5dsigma*6psigma] excited state of [Au(3)(dcmp)(2)](3+) and the counterions. In solid state, complex [Ag(3)(dcmp)(2)][ClO(4)](3) (6) displays an intense emission band at 375 nm with a Stokes shift of approximately 7200 cm(-1) from the (1)[4dsigma*-->5psigma] absorption band at 295 nm. The 375 nm emission band is assigned to the emission directly from the (3)[4dsigma(*)5psigma] excited state of 6. Density functional theory (DFT) calculations revealed that the absorption and emission energies are inversely proportional to the number of metal ions (n) in polynuclear Au(I) and Ag(I) linear chain complexes without close metalanion contacts. The emission energies are extrapolated to be 715 and 446 nm for the infinite linear Au(I) and Ag(I) chains, respectively, at metalmetal distances of about 2.93-3.02 A. A QM/MM calculation on the model [Au(3)(dcmp)(2)Cl(2)](+) system, with Au...Cl contacts of 2.90-3.10 A, gave optimized Au...Au distances of 2.99-3.11 A in its lowest triplet excited state and the emission energies were calculated to be at approximately 600-690 nm, which are assigned to a three-coordinate Au(I) site with its spectroscopic properties affected by Au(I)...Au(I) interactions.

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Absorption Spectra of Several Metal Complexes Revisited by the Time-Dependent Density-Functional Theory-Response Theory Formalism

Cited by 97 publications

References 49 publications

Quantitatively Correct UV-vis Spectrum of Ferrocene with TDB3LYP

Quantitatively Correct UV-vis Spectrum of Ferrocene with TDB3LYP

Multi-configuration time-dependent density-functional theory based on range separation

The ³[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

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Absorption Spectra of Several Metal Complexes Revisited by the Time-Dependent Density-Functional Theory-Response Theory Formalism

Cited by 97 publications

References 49 publications

Quantitatively Correct UV-vis Spectrum of Ferrocene with TDB3LYP

Quantitatively Correct UV-vis Spectrum of Ferrocene with TDB3LYP

Multi-configuration time-dependent density-functional theory based on range separation

The 3[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands

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The ³[ndσ*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains with Bridging Phosphine Ligands