A complete experimental assessment of Franck-Condon structural effects for an irreversible outer-sphere electron-transfer reaction: applications of time-dependent Raman scattering theory to the one-electron reduction of 4-cyano-N-methylpyridinium

Blackbourn, Robert L.; Johnson, Christopher; Hupp, Joseph T.; Bryant, Mark A.; Sobocinski, Raymond L.; Pemberton, Jeanne E.

doi:10.1021/j100179a004

Cited by 27 publications

(18 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Obviously, both A-term and B-term scattering regimes 14,17,29,30 can be responsible for these results but the A-type contribution is probably important, as inferred by the observation of some overtone and combination bands and the very large Raman enhancements in the first group of modes. However, whatever the investigated vibration, the maxima in the REPs do not show any significant wavelength shift and the enhancements of so many modes are in favor of another mechanism due to a B-term scattering or vibronic coupling process.…”

Section: Resonance Raman Effects and Raman Excitation Profiles (Reps)mentioning

confidence: 95%

Infrared, Raman and resonance Raman spectra of the solid nickel(II) thiophosphate compound (PPh4)3 [(NiPS4)3] and force constants in the trinickel [Ni3P3S12]3− cyclic anion

Sourisseau¹,

Rodriguez²,

Jobic³

et al. 1999

J. Raman Spectrosc.

View full text Add to dashboard Cite

The UV-visible (350-900 nm), infrared and Raman (30-800 cm −1 ) spectra of a new transition metal thiophosphate solid compound, (PPh 4 ) 3 [(NiPS 4 ) 3 ], were analyzed using powder samples. Electronic transitions of the 1 F 2 → 1 A 1 type originating in the (PS 4 ) 3− groups were detected from visible absorbance measurements in the 440-520 nm range and most of the expected infrared and Raman vibrational modes of the trimetallic ring anion [Ni 3 P 3 S 12 ] 3− were observed in the 600-30 cm −1 region. Also, resonance Raman spectra were recorded using exciting radiation of several wavelengths in the 680-450 nm range and the Raman excitation profiles of several fundamentals were established: they all peak near 488 nm and exhibit the strongest enhancements for totally symmetric and non-totally symmetric stretching and bending modes of (NiS 4 ) groups. It is therefore concluded that several ligand to metal charge-transfer electronic transitions are overlapped and involved in vibronic coupling mechanisms. Furthermore, the vibrational assignments were checked by a valence force field calculation for an isolated [Ni 3 P 3 S 12 ] 3− anion of C 3v symmetry. The potential energy distributions and mean squared vibrational amplitudes revealed strong n(Ni-S) and d(S-P-S) couplings and relatively high n(Ni-S) stretching modes at near 310 cm−1 . Compared with results in the one-dimensional KNiPS 4 compound containing infinite anionic chains 1 1 [NiPS 4 ] − , one notes a force constant increase on the P-S exocyclic (m 1 ) bonds, no change on the bridged (m 2 and m 3 ) P-S bonds and a slight increase in the Ni-S stretching force constants varying from 75 to 85 N m −1 in accordance with a localized ligand to metal charge-transfer mechanism. Hence a comparison of the induced Raman scattering processes in the (PPh 4 ) 3 [(NiPS 4 ) 3 ] and KNiPS 4 solid compounds shows that the ligand to metal charge transfers and the crystal field effects have a strong influence on the vibrational properties in these thiophosphate compounds.

show abstract

Section: Resonance Raman Effects and Raman Excitation Profiles (Reps)mentioning

confidence: 95%

Infrared, Raman and resonance Raman spectra of the solid nickel(II) thiophosphate compound (PPh4)3 [(NiPS4)3] and force constants in the trinickel [Ni3P3S12]3− cyclic anion

Sourisseau¹,

Rodriguez²,

Jobic³

et al. 1999

J. Raman Spectrosc.

View full text Add to dashboard Cite

show abstract

“…First, resonance ground state FSRS, which uses only the Raman pump and probe pulses, can be used to identify modes which drive the complexes out of the initial Franck-Condon region on the excited state surface. [40][41][42][43] Since the transfer occurs on a rapid B100 fs timescale, it is logical to assume that these initial motions out of the Franck-Condon region are those that drive the electron transfer process.…”

Section: Excited State Isomerization In Phytochromementioning

confidence: 99%

Probing structural evolution along multidimensional reaction coordinates with femtosecond stimulated Raman spectroscopy

Frontiera

Fang

Dasgupta

et al. 2012

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Mapping out multidimensional potential energy surfaces has been a goal of physical chemistry for decades in the quest to both predict and control chemical reactivity. Recently a new spectroscopic approach called Femtosecond Stimulated Raman Spectroscopy or FSRS was introduced that can structurally interrogate multiple dimensions of a reactive potential energy surface. FSRS is an ultrafast laser technique which provides complete time-resolved, background-free Raman spectra in a few laser shots. The FSRS technique provides simultaneous ultrafast time (~50 fs) and spectral (~8 cm(-1)) resolution, thus enabling one to follow reactive structural evolutions as they occur. In this perspective we summarize how FSRS has been used to follow structural dynamics and provide mechanistic detail on three classical chemical reactions: a structural isomerization, an electron transfer reaction, and a proton transfer reaction.

show abstract

“…These results will also provide a useful reference to which more sophisticated simulations can be compared to assess the relative importance of effects such as changes in the transition dipole moment with vibrational coordinate and anharmonicity on the resonance Raman and absorption spectra. The resonance Raman intensities and absorption spectra were calculated using a time-dependent formalism. − The absorption cross sections were computed from and the resonance Raman cross sections were calculated from where n is the solvent index of refraction, M is the transition length evaluated at the equilibrium geometry, E L is the incident photon energy, E S is the scattered photon energy, f is the final state for the resonance Raman process, ε f is the energy of the ground-state energy level | f 〉, and δ( E L +ε i − E S −ε f ) is a delta function to sum up cross sections with the same frequency. P i is the initial Boltzmann population of the ground-state energy level | i 〉 which has energy ε i .…”

Section: Calculationsmentioning

confidence: 99%

Resonance Raman Investigation of the Au(I)−Au(I) Interaction of the ¹[dσ*pσ] Excited State of Au₂(dcpm)₂(ClO₄)₂ (dcpm = Bis(dicyclohexylphosphine)methane)

et al. 1999

View full text Add to dashboard Cite

We present a resonance Raman investigation of the lowest energy dipole-allowed absorption band of [Au 2 (dcpm) 2 ](ClO 4 ) 2 (dcpm ) bis(dicyclohexylphosphine)methane). The resonance Raman spectra provide the first experimental proof of the 5dσ* f 6pσ electronic transition in dinuclear gold(I)-phosphine compounds. A resonance Raman intensity analysis of the spectra allows estimation of the structural changes of the [dσ*pσ] excited states relative to the ground state.

show abstract

A complete experimental assessment of Franck-Condon structural effects for an irreversible outer-sphere electron-transfer reaction: applications of time-dependent Raman scattering theory to the one-electron reduction of 4-cyano-N-methylpyridinium

Cited by 27 publications

References 0 publications

Infrared, Raman and resonance Raman spectra of the solid nickel(II) thiophosphate compound (PPh4)3 [(NiPS4)3] and force constants in the trinickel [Ni3P3S12]3− cyclic anion

Infrared, Raman and resonance Raman spectra of the solid nickel(II) thiophosphate compound (PPh4)3 [(NiPS4)3] and force constants in the trinickel [Ni3P3S12]3− cyclic anion

Probing structural evolution along multidimensional reaction coordinates with femtosecond stimulated Raman spectroscopy

Resonance Raman Investigation of the Au(I)−Au(I) Interaction of the ¹[dσ*pσ] Excited State of Au₂(dcpm)₂(ClO₄)₂ (dcpm = Bis(dicyclohexylphosphine)methane)

Contact Info

Product

Resources

About

A complete experimental assessment of Franck-Condon structural effects for an irreversible outer-sphere electron-transfer reaction: applications of time-dependent Raman scattering theory to the one-electron reduction of 4-cyano-N-methylpyridinium

Cited by 27 publications

References 0 publications

Infrared, Raman and resonance Raman spectra of the solid nickel(II) thiophosphate compound (PPh4)3 [(NiPS4)3] and force constants in the trinickel [Ni3P3S12]3− cyclic anion

Infrared, Raman and resonance Raman spectra of the solid nickel(II) thiophosphate compound (PPh4)3 [(NiPS4)3] and force constants in the trinickel [Ni3P3S12]3− cyclic anion

Probing structural evolution along multidimensional reaction coordinates with femtosecond stimulated Raman spectroscopy

Resonance Raman Investigation of the Au(I)−Au(I) Interaction of the 1[dσ*pσ] Excited State of Au2(dcpm)2(ClO4)2 (dcpm = Bis(dicyclohexylphosphine)methane)

Contact Info

Product

Resources

About

Resonance Raman Investigation of the Au(I)−Au(I) Interaction of the ¹[dσ*pσ] Excited State of Au₂(dcpm)₂(ClO₄)₂ (dcpm = Bis(dicyclohexylphosphine)methane)