“…One of the earliest Raman intensity analyses to make use of the time-domain picture of resonance Raman scattering was the work of Yang and Zink on the MLCT (CrfNO) transition of K 3 [Cr(CN) 5 -NO]. 72 They used a simple formula, analogous to eq 7, to calculate the displacement in the dominant Cr-N stretching mode from its fundamental to overtone intensity ratio. They then used eq 7 to determine the displacements in three other modes that clearly exhibited only fundamentals and showed that these four modes alone with their Ramandetermined displacements gave a reasonable representation of the lower energy region of the absorption spectrum.…”
Section: A Metal-to-ligand and Ligand-to-metal Charge Transfer Transi...mentioning
“…One of the earliest Raman intensity analyses to make use of the time-domain picture of resonance Raman scattering was the work of Yang and Zink on the MLCT (CrfNO) transition of K 3 [Cr(CN) 5 -NO]. 72 They used a simple formula, analogous to eq 7, to calculate the displacement in the dominant Cr-N stretching mode from its fundamental to overtone intensity ratio. They then used eq 7 to determine the displacements in three other modes that clearly exhibited only fundamentals and showed that these four modes alone with their Ramandetermined displacements gave a reasonable representation of the lower energy region of the absorption spectrum.…”
Section: A Metal-to-ligand and Ligand-to-metal Charge Transfer Transi...mentioning
“…Several research groups have used resonance Raman intensity analysis in order to determine the vibrational reorganizational energies of many different photoinduced electron-transfer reactions which have diffuse charge transfer electronic transitions such as metal to ligand charge transfer (MLCT), ligand to ligand charge transfer (LLCT), intervalence transitions of inorganic compounds, organic noncovalent donor-acceptor complexes charge transfer transitions, and very recently an organic covalent donoracceptor compound. [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] In this paper we present a resonance Raman intensity analysis of the MLCT absorption at ∼344 nm for [Pt(dppm) 2 -(PhCtC) 2 ] in dichloromethane solution and of the MMLCT absorption band at ∼393 nm for [Pt 2 (µ-dppm) 2 (µ-PhCtC)-(PhCtC) 2 ] + in acetonitrile solution. We have taken resonance Raman spectra including absolute Raman cross section measurements at five excitation wavelengths for [Pt(dppm) 2 -(PhCtC) 2 ] and at six excitation wavelengths for [Pt 2 (µ-dppm) 2 (µ-PhCtC)(PhCtC) 2 ] + .…”
Section: Introductionmentioning
confidence: 99%
“…The rates of electron transfer reactions are determined in part by the reorganization energies among the different vibrational modes of the molecules involved in the electron transfer. − The vibrational reorganizational energies in the case of electron-transfer reactions that take place directly upon absorption of light (DA + h ν → D + A - ) can sometimes be obtained from the electron charge-transfer absorption and/or emission spectra. − Many charge-transfer absorption bands do not have vibrational resolution (especially in room temperature solutions), and in many cases it is not possible to elucidate the vibrational reorganizational energies directly from the absorption and/or fluorescence spectra. Several research groups have used resonance Raman intensity analysis in order to determine the vibrational reorganizational energies of many different photoinduced electron-transfer reactions which have diffuse charge transfer electronic transitions such as metal to ligand charge transfer (MLCT), ligand to ligand charge transfer (LLCT), intervalence transitions of inorganic compounds, organic noncovalent donor−acceptor complexes charge transfer transitions, and very recently an organic covalent donor−acceptor compound. − …”
We report resonance Raman spectra including absolute Raman cross section measurements obtained with excitation wavelengths within the MLCT absorption band of [Pt(dppm) 2 (PhCtC) 2 ] and the MMLCT absorption band of [Pt 2 (µ-dppm) 2 (µ-PhCtC)(PhCtC) 2 ] + . We have simultaneously simulated the absolute absorption and resonance Raman intensities in order to estimate the vibrational reorganizational energies associated with the MLCT and MMLCT transitions. We observe a small amount of fluorescence background underneath the resonance Raman spectra of [Pt(dppm) 2 (PhCtC) 2 ] which we attribute to emission from the very shortlived initially excited MLCT state. Our quantum yield measurements of this fluorescence yields an excited state lifetime of approximately 80-130 fs.
“…Due to the reasonable complexities of the examined molecules the short time dynamic limit (see Section 2) is appropriate to establish the values for compounds with MLCT transitions [73,74].…”
Section: Evaluation Of Using the Resonance Excitation Profiles And Thmentioning
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