Time-resolved resonance raman spectroscopy: A retrospect on the early days

Wilbrandt, R.

doi:10.1002/(sici)1520-6343(1996)2:5<263::aid-bspy1>3.0.co;2-6

Cited by 8 publications

(19 citation statements)

References 32 publications

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“…This realisation cued the development of spectroscopic techniques such as time-resolved infrared (TRIR) 2 and time-resolved resonance Raman (TR 3 ). 3 TRIR combines UV-Vis flash photolysis with fast IR detection and is a particularly powerful technique for the study of compounds containing carbonyl ligands. 4 This is due to the high oscillator strengths of ν(CO) stretching vibrations and the sensitivity of their energy and bandwidth to changes in electronic structure, which allow the CO ligands to act as † Dedicated to the memory of Nobel Laureate, Lord George Porter FRSC FRS OM.…”

Section: Introductionmentioning

confidence: 99%

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The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN: a comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study

Dyer

Blau

Coates

et al. 2003

Photochem Photobiol Sci

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The photophysical properties of fac-[Re(CO)3(dppz)(py)]+ (1, where dppz = dipyrido[3,2-a: 2',3'-c]phenazine) in CH3CN have been investigated using a series of complementary techniques including visible and infrared transient absorption and resonance Raman spectroscopy on the picosecond and nanosecond timescales. The results confirm previous reports that the lowest-lying emissive state in 1 is a triplet intra-ligand (3IL) state localised on the dppz ligand and have provided detailed information on the dynamics of 1 upon photoexcitation, including the relative energies of the excited state species encountered and the electronic distribution within these. If the dppz ligand is viewed in terms of phenanthroline (phen) and phenazine (phz) moieties, the emissive state is probably more accurately described as a 3 pi-->pi *(phz) IL state. The picosecond studies have shown that this emissive state is formed, at least in part, within 30 ps of excitation from a precursor, which is possibly a 3 pi-->pi *(phen) IL state. On the nanosecond timescale, TRIR has been employed to elucidate further dynamics and reveal the presence of an energetically close-lying state in equilibrium with the emissive state. This has tentatively been assigned as being 3d pi(Re)-->pi *(phz) metal-to-ligand charge transfer (MLCT) in nature. A summary of the photophysics is proposed in the form of a Jablonski scheme. Time dependent density functional theory (TD-DFT) calculations support the relative ordering and suggested electronic character of the excited state species involved.

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Section: Introductionmentioning

confidence: 99%

“…TR 3 uses an initial photoexcitation pulse and then a time delayed probe beam, at a wavelength that matches a molecular electronic absorption band of the transient species, to generate the resonance Raman spectrum. This resonance greatly enhances the Raman signals of particular vibronic modes of the molecule under study.…”

Section: Introductionmentioning

confidence: 99%

The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN: a comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study

Dyer

Blau

Coates

et al. 2003

Photochem Photobiol Sci

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“…Much effort has been devoted over the years to circumvent this fundamental limitation. Up until recently, the most successful approach was based on picosecond or femtosecond time‐resolved Raman spectroscopy and utilizes the fact that Raman scattering is instantaneous, while fluorescence is delayed (with fluorescence lifetimes ranging typically in the picosecond to tens of nanoseconds range). On top of the obvious increase in experimental complexity, time‐resolved methods also have limitations in terms of spectral resolution and are challenging to apply to fluorophores with more moderate QYs (and therefore shorter fluorescence lifetimes).…”

Section: Introductionmentioning

confidence: 99%

CW measurements of resonance Raman profiles, line‐widths, and cross‐sections of fluorescent dyes: application to Nile Blue A in water and ethanol

Reigue

Auguié

Etchegoin

et al. 2013

J Raman Spectroscopy

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The aim of this work is to illustrate the power of recently developed methods for measuring resonance Raman scattering (RRS) spectra of efficient fluorophores (using a standard continuous wave excitation and a charge-coupled device (CCD)-based Raman spectrometer), by applying them to a detailed study of a specific fluorophore: Nile Blue A. A combination of methods are used to measure the RRS properties of Nile Blue A in water (quantum yield (QY) of 4%) and ethanol (QY of 22%) at excitation wavelengths between 514 and 647 nm, thus covering both pre-resonance and RRS conditions. Standard Raman measurements are used in situations where the fluorescence background is small enough to clearly observe the Raman peaks, while the recently introduced polarization-difference RRS and continuously shifted Raman scattering are used closer to (or at) resonance. We show that these relatively straightforward methods allow us to determine the Raman cross-sections of the most intense Raman peaks and provide an accurate measurement of their line-width; even for broadenings as low as $ 4 cm À 1 . Moreover, the obtained Raman excitation profiles agree well with those derived from the optical absorption by a simple optical transform model. This study demonstrates the possibility of routine RRS measurements using standard Raman spectrometers, as opposed to more complicated time-resolved techniques. /journal/jrs Ω ¼ 1:8 Â 10 À25 cm 2 /sr) is inferred as for CSRS with respect to the fluorescence background intensity (from an independent measurement of the fluorescence cross-section). Assuming the Raman depolarization ratio is r R = 1/3, the Raman cross-section is then deduced from [6] Measuring resonance Raman spectra of fluorophores

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“…The technical and scientific growth using TR3 as a technique has been reported from time to time in past few decades. [28][29][30][31][32][33][34][35][36][37][38][39][40][41]…”

Section: Introductionmentioning

confidence: 99%

Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

2011

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The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single "do-it-all" technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-μs) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy.

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Time-resolved resonance raman spectroscopy: A retrospect on the early days

Abstract: The early development of time‐resolved resonance Raman spectroscopy during the late 1970s and beginning of the 1980s is reviewed. © 1996 John Wiley & Sons, Inc.

Cited by 8 publications

References 32 publications

The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN: a comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study

The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN: a comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study

CW measurements of resonance Raman profiles, line‐widths, and cross‐sections of fluorescent dyes: application to Nile Blue A in water and ethanol

Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

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