Femtosecond Multicolor Pump−Probe Study of Ultrafast Electron Transfer of [(NH3)5RuIIINCRuII(CN)5]- in Aqueous Solution

Son, Dong Hee; Kambhampati, Patanjali; Kee, Tak W.; Barbara, Paul F.

doi:10.1021/jp014151f

Cited by 71 publications

(69 citation statements)

References 41 publications

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“…Such biphasic dynamics is rather typical for ultrafast ground state recovery upon CT excitation [17,18]. Excitation in the CT band is followed by an ultrafast internal conversion to the vibrationally hot electronic ground state, which is then thermalized by vibrational cooling.…”

Section: Ultrafast Processes In the Fessa Complexmentioning

confidence: 98%

Photochemistry of Fe(III) and sulfosalicylic acid aqueous solutions

Pozdnyakov

Plyusnin

Grivin

et al. 2006

Journal of Photochemistry and Photobiology A: Chemistry

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Femtosecond and nanosecond laser flash photolysis was used to determine the photophysical and photochemical processes in aqueous solutions of Fe(III) ion and 5-sulfosalicylic acid (SSA) containing the FeSSA complex and the free ligand. Excitation of the FeSSA complex in the charge transfer band (λ max = 505 nm) is followed by an ultrafast relaxation to the ground electronic state with two characteristic times of 0.26 and 1.8 ps.The shorter time constant is ascribed to internal conversion to the vibrationally hot electronic ground state of FeSSA and the 1.8 ps time constant is assigned to the vibrational cooling of the ground state. The UV irradiation of the solution (308 nm) leads to the excitation of both the free ligand and the FeSSA complex. The latter relaxes rapidly and the free ligand undergoes intersystem crossing to the triplet state. This system undergoes an irreversible photochemical reaction originating from an electron transfer (k = (9 ± 2) × 10 8 M −1 s −1 ) from the free ligand in the triplet state to the FeSSA complex. This electron transfer is accompanied by an energy transfer between these species (k = (1.3 ± 0.2) × 10 9 M −1 s −1 ).

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Section: Ultrafast Processes In the Fessa Complexmentioning

confidence: 98%

Photochemistry of Fe(III) and sulfosalicylic acid aqueous solutions

Pozdnyakov

Plyusnin

Grivin

et al. 2006

Journal of Photochemistry and Photobiology A: Chemistry

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“…This is one of several complexes containing two or more metal centers with different oxidation states that have served as model systems in both steady-state and time-resolved spectroscopic experiments to probe the coupling between electronic and vibrational motions during ultrafast electron transfer reactions. [17][18][19][20][21][22][23][24][25] Transient IR, optical, and resonance Raman studies of FeRu in polar solvents have suggested the 7 involvement of some of the high frequency ν CN vibrations in the charge transfer process 19,23 and significant excitation in the ν CN modes upon ultrafast back electron transfer. 22 We have extensively studied the vibrational anharmonic couplings among ν CN modes and the role of solvent in modulating the molecular structure, anharmonic couplings, and the oxidation states of the metals in the FeRu complex.…”

mentioning

confidence: 99%

Measuring Coherently Coupled Intramolecular Vibrational and Charge-Transfer Dynamics with Two-Dimensional Vibrational–Electronic Spectroscopy

Courtney

Fox

Estergreen

et al. 2015

J. Phys. Chem. Lett.

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We demonstrate Fourier transform (FT) 2D vibrational-electronic (2D VE) spectroscopy employing a novel mid-IR and optical pulse sequence. This new femtosecond third-order nonlinear spectroscopy provides the high time and frequency resolutions of existing 2D FT techniques; however, resulting 2D VE spectra contain IR and electronic dipole moment cross terms. We use 2D VE spectroscopy to help understand the vibrational-electronic couplings in the cyanide-bridged transition-metal mixed valence complex [(CN)5Fe(II)CNRu(III)(NH3)5](-) dissolved in formamide. The amplitudes of the cross-peaks in the 2D VE spectra reveal that three of the intramolecular cyanide stretching vibrations lying along the charge-transfer axis are coherently coupled to the metal-to-metal charge-transfer electronic transition with differing strengths. Analysis of the 2D VE line shapes reveals positive and negative correlations of the cyanide stretching modes with the charge-transfer transition depending on the physical orientation of the vibration in the molecule and its interaction with the solvent. The insights found thus far into the vibronic couplings in the mixed valence model system indicate that the 2D VE technique will be a valuable addition to the existing multidimensional spectroscopy toolbox.

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“…We note that impulsively excited lowfrequency modes in the 70-600 cm −1 region have been previously observed in femtosecond transient absorption experiments on prussian blue and dinuclear transition metal mixed valence compounds. [32][33][34][35] The role of coupled electronic and nuclear motions in ultrafast photoinduced chemical reactions was brought to the forefront when vibrationally coherent photochemistry was observed in rhodopsin almost twenty years ago. 36 To explore how vibrational relaxation in high frequency vibrations affects ultrafast charge transfer processes, we performed fifthorder transient IR DPP spectroscopy at multiple time points during a photoinduced BET reaction in a trinuclear cyanobridged mixed-valence complex.…”

mentioning

confidence: 99%

Communication: Probing non-equilibrium vibrational relaxation pathways of highly excited C≡N stretching modes following ultrafast back-electron transfer

Lynch

Slenkamp

Khalil

2012

The Journal of Chemical Physics

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Fifth-order nonlinear visible-infrared spectroscopy is used to probe coherent and incoherent vibrational energy relaxation dynamics of highly excited vibrational modes indirectly populated via ultrafast photoinduced back-electron transfer in a trinuclear cyano-bridged mixed-valence complex. The flow of excess energy deposited into four C≡N stretching (νCN) modes of the molecule is monitored by performing an IR pump-probe experiment as a function of the photochemical reaction (τvis). Our results provide experimental evidence that the nuclear motions of the molecule are both coherently and incoherently coupled to the electronic charge transfer process. We observe that intramolecular vibrational relaxation dynamics among the highly excited νCN modes change significantly en route to equilibrium. The experiment also measures a 7 cm−1 shift in the frequency of a ∼57 cm−1 oscillation reflecting a modulation of the coupling between the probed high-frequency νCN modes for τvis < 500 fs.

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Femtosecond Multicolor Pump−Probe Study of Ultrafast Electron Transfer of [(NH₃)₅Ru^IIINCRu^II(CN)₅]^- in Aqueous Solution

Cited by 71 publications

References 41 publications

Photochemistry of Fe(III) and sulfosalicylic acid aqueous solutions

Photochemistry of Fe(III) and sulfosalicylic acid aqueous solutions

Measuring Coherently Coupled Intramolecular Vibrational and Charge-Transfer Dynamics with Two-Dimensional Vibrational–Electronic Spectroscopy

Communication: Probing non-equilibrium vibrational relaxation pathways of highly excited C≡N stretching modes following ultrafast back-electron transfer

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