Hole-burning spectroscopy

Note that the same concept could be used differently If molecules that are excited by the first light beam fluoresce, we would expect the fluorescence spectrum observed following such excitation to be considerably narrower than what would be nonnally observed after exciting the full inhomogeneous band. 

Both this fluorescence line narrowing and hole burning spectroscopy are conceptually trivial. Still, they can provide very useful information on the homogeneously broadened lines as illustrated in Fig. 18.11. What makes life less simple and more interesting is that other dynamical effects can express themselves in this 

Finally, even if small amplitude configuration changes about the chromophore molecules are not sufficient for filling up the hole on the experimental lifetime. 

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Pump-probe absorption experiments on the femtosecond time scale generally fall into two effective types, depending on the duration and spectral width of the pump pulse. If tlie pump spectrum is significantly narrower in width than the electronic absorption line shape, transient hole-burning spectroscopy [101. 102. 103. 104. 105. 106. 107. 108. 109. 110. 111. 112 and 113] can be perfomied. The second type of experiment, dynamic absorption spectroscopy [57, 114. 115. 116. 117. 118. 119. 120. 121 and 122], can be perfomied if the pump and probe pulses are short compared to tlie period of the vibrational modes that are coupled to the electronic transition. 

Figure B2.1.6 Femtosecond spectrometer for transient hole-burning spectroscopy with a continuum probe. Symbols used bs, 10% reflecting beamsplitter p, polarizer. The continuum generator consists of a focusing lens, a cell containing flowing water or ethylene glycol or, alternatively, a sapphire crystal and a recollimating lens.

Kovalenko S A, Ernsting N P and Ruthmann J 1996 Femtosecond hole-burning spectroscopy of the dye DCM in solution the transition from the locally excited to a charge-transfer state Chem. Phys. Lett. 258 445-54... 

Riesen H (2004) Progress in Hole-Burning Spectroscopy of Coordination Compounds 107 179-205... 

Walsh RJ, Reinot T, Hayes JM et al (2002) Nonphotochemical hole burning spectroscopy of a mitochondrial selective rhodamine dye molecule in normal and cancerous ovarian surface epithelial cells. J Lumin 98 115-121... 

Laser-induced multiphoton ionization and hole burning spectroscopy... 

Pairwise EET rates cannot be directly measured in antenna systems. The closest approach to direct determination is offered on the one hand by time resolved picosecond and sub-picosecond absorption and fluorescence measurements and on the other hand by hole burning spectroscopies. Time resolved techniques do not detect transfer between isoenergetic sites. A somewhat more indirect approach to determining pairwise rates is that of analysing excited state lifetime data in terms of a particular antenna and an EET model. 

Optical Spectroscopy General principles and overview, 246, 13 absorption and circular dichroism spectroscopy of nucleic acid duplexes and triplexes, 246, 19 circular dichroism, 246, 34 bioinorganic spectroscopy, 246, 71 magnetic circular dichroism, 246, 110 low-temperature spectroscopy, 246, 131 rapid-scanning ultraviolet/visible spectroscopy applied in stopped-flow studies, 246, 168 transient absorption spectroscopy in the study of processes and dynamics in biology, 246, 201 hole burning spectroscopy and physics of proteins, 246, 226 ultraviolet/visible spectroelectrochemistry of redox proteins, 246, 701 diode array detection in liquid chromatography, 246, 749. 

Fig. 2 Pulse sequences for a - regular T2D-IR spectroscopy, b - transient 2D hole burning spectroscopy, c - T2D-IR in the band labeling mode.

We have done a study by time-resolved hole-burning spectroscopy for dye molecules in polar solvents and found that the time correlation function of the hole width decays much slower than that of the peak shift of the hole, which occurs very rapidly, as you observed in the case of the fluorescence Stokes shift [K. Nishiyama, Y. Asano, N. Hashimoto, and T. Okada, J. Mol. Liquids 65/66, 41 (1995)]. 

Progress in Hole-Burning Spectroscopy of Coordination Compounds... 

Laenen R, Rauscher C. Transient hole-burning spectroscopy of associated ethanol molecules in the infrared structural dynamics and evidence for energy migration. J Chem Phys 1997 106 1-7. 

Nir E, Janzen C, Imhof P, Kleinermanns K, de Vries MS (2001) Guanine tautomerism revealed by UV-UV and IR-UV hole burning spectroscopy. Journal of Chemical Physics 115 4604 1611. 

Scherzer, W. Kraetzschmar, O. Selzle, H. L. Schlag, E. W. Structural isomers of the benzene dimer from mass selective hole-burning spectroscopy, Z. Naturforsch. A 1992,47, 1248-1252. 

Solvation Dynamics of Dye Molecules in Polar Solvents Studied by Time Resolved Hole Burning Spectroscopy... 

The very first fluorescence spectra of jet-cooled exciplexes indicated the existence of two types of ground-state van der Waals adducts. For instance, the anthracene-dimethylaniline system displayed two types of cluster bands in the fluorescence excitation spectrum broad ( 150 cm ) and structureless, leading to typical ex-ciplex emission, and narrow (1 cm ), leading to resonance-type emission [10, 20]. It was assumed that they are due to different 1 1 adducts, distinguished by different geometries. Recently, laser-based techniques were developed that allow the discrimination of different species. One is hole-burning spectroscopy and another— mass-selected photoionization. 

Figure 2. Characterization of intermolecular exci-plexes by hole-burning spectroscopy. Adapted from Ref. [22a] (a) Fluorescence excitation ( emission set at 375 nm) and (b) hole-burning spectra of the R-isomer of the anthracene-dimethylaniline (An-DMA) adduct in a supersonic jet. The probe laser was tuned on the most intense line of the adduct. Lines marked with asterisks are due to bare anthracene, (c) Fluorescence excitation ( emission set at 450 nm) and (d) hole-burning spectra of the E-isomer of the An- DMA adduct in a supersonic jet. The probe laser was tuned to the maximum of the broad exciplex excitation band.

Several linked molecules in which the donor is an aniline derivative and the acceptor an anthracene moiety were investigated. In the case of anthracene linked to V,V-dimethylaniline by a trimethylene bridge, two molecules were investigated. In both the link was to the meta (3-) position of the aniline. In one anthracene was linked in the 9-position, (9-anthryl)-3-[w-(A, A -dimethylamino)phenyl] propane (9-An-m-DMA), and in the other the link was to the 1-position (1-An-w-DMA). In both cases hole-burning spectroscopy revealed two distinct species, that were assigned to two isomeric forms (possible structures are shown in Scheme 1). The emission spectra of both forms at the origin bands were essentially of the locally excited type. As the internal energy was increased, the exciplex emission spectrum... 

The complex formation between ANI and ammonia clusters has been investigated by using mass resolved excitation spectroscopy (MRES), hole burning spectroscopy (HB)268 and IR spectroscopy coupled to different ionization spectroscopies269-271. Rotational spectra of these complexes are not reported yet. Some ab initio calculations on both neutral and ionized complexes are available269 272-274. In this case, the most stable form of the neutral ANI-NH3 complex is a consequence of a hydrogen bond between a NH bond of aniline... 

A treatment for analysing the excitation and fluorescence multiwavelength polarized decay surfaces has been given for the case of a mixture of noninteracting species. An improved model for analysis of fluorescence anisotropy measurements has been presented. Limitations to the use of intense excitation pulses in fluorescence and thermal lens spectrophotometers are discussed in terms of optical saturation. Such artefacts can be eliminated by reference to the fluorescence quantum yield of Rhodamine 6G. A model has been given to describe spectral diffusion in time-resolved hole-burning spectroscopy. ... 

Offermans T., Meskers S. C. J. and Janssen R. A. J. (2003), Charge recombination in a poly(para-phenylenevinylene)-fullerene derivative composite film studied by transient, nonresonant, hole-burning spectroscopy , J. Chem. Phys. 119, 10924-10929. 

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