Laser spectroscopy excitation

This spectrum is called a Raman spectrum and corresponds to the vibrational or rotational changes in the molecule. The selection rules for Raman activity are different from those for i.r. activity and the two types of spectroscopy are complementary in the study of molecular structure. Modern Raman spectrometers use lasers for excitation. In the resonance Raman effect excitation at a frequency corresponding to electronic absorption causes great enhancement of the Raman spectrum. 

While a laser beam can be used for traditional absorption spectroscopy by measuring / and 7q, the strength of laser spectroscopy lies in more specialized experiments which often do not lend themselves to such measurements. Other techniques are connnonly used to detect the absorption of light from the laser beam. A coimnon one is to observe fluorescence excited by the laser. The total fluorescence produced is nonnally proportional to the amount of light absorbed. It can be used as a measurement of concentration to detect species present in extremely small amounts. Or a measurement of the fluorescence intensity as the laser frequency is scaimed can give an absorption spectrum. This may allow much higher resolution than is easily obtained with a traditional absorption spectrometer. In other experiments the fluorescence may be dispersed and its spectrum detennined with a traditional spectrometer. In suitable cases this could be the emission from a single electronic-vibrational-rotational level of a molecule and the experimenter can study how the spectrum varies with level. 

Upon absorption of UV radiation from sunlight the bases can proceed through photochemical reactions that can lead to photodamage in the nucleic acids. Photochemical reactions do occur in the bases, with thymidine dimerization being a primary result, but at low rates. The bases are quite stable to photochemical damage, having efficient ways to dissipate the harmful electronic energy, as indicated by their ultrashort excited state lifetimes. It had been known for years that the excited states were short lived, and that fluorescence quantum yields are very low for all bases [4, 81, 82], Femtosecond laser spectroscopy has, in recent years, enabled a much... 

The following case study contains examples of several topics discussed in previous sections, including some aspects of laser technology, laser spectroscopy and laser chemistry. A variety of lasers and laser techniques are applied in a straightforward manner to the problem of ascertaining structural and dynamical information on an excited electronic state of wide chemical interest. This information is obtained rather simply, illustrating the potential of laser techniques in the resolution of problems in solution chemistry. 

The most notable feature of these intrazeolite photooxygenations (Fig. 30) is that the oxygen CT band experiences a dramatic bathochromic shift in comparison to solution. This was detected initially by recording the product growth as a function of irradiation wavelength (laser reaction excitation spectrum)98,110 and was later verified by direct observation using diffuse reflectance UV-Vis spectroscopy.111 For example, 2,3-dimethyl-2-butene CT-absorbance is shifted to lower energy by more than 300 nm... 

An interesting and powerful new development in Raman spectroscopy of catalysts is the use of a UV laser to excite the sample. This has two major advantages. First, the scattering cross section, which varies with the fourth power of the frequency, is substantially increased. Second, the Raman peaks shift out of the visible region of the spectrum where fluorescence occurs. The reader is referred to Li and Stair for applications of UV Raman spectroscopy on catalysts [40]. 

P. A. Johnson, T. E. Barba , B. W. Smith, and J. D. Winefordner, Ultralow detection limits for an organic dye determined by fluorescence spectroscopy with laser diode excitation, Anal. Chem. 61, 861-863 (1989). 

When molecules absorb a photon and produce an electronic excited state, the energy can be dissipated in several ways luminescence, radiationless decay to the ground state, and photochemistry. Luminescence dominated the older literature because it was easy to observe. A good review of luminescence is in Volume 3 of David Dolphin s seven-volume series The Porphyrins. Picosecond laser spectroscopy allowed for exploration of the radiationless decay pathways, particularly the initial steps that compete with luminescence and lead to photochemistry. Two principal forms of radiationless decay lead to long-term metastables ligand ejection and electron transfer. 

An intense femtosecond laser spectroscopy-based research focusing on the fast relaxation processes of excited electrons in nanoparticles has started in the past decade. The electron dynamics and non-linear optical properties of nanoparticles in colloidal solutions [1], thin films [2] and glasses [3] have been studied in the femto- and picosecond time scales. Most work has been done with noble metal nanoparticles Au, Ag and Cu, providing information about the electron-electron and electron-phonon coupling [4] or coherent phenomenon [5], A large surface-to-volume ratio of the particle gives a possibility to investigate the surface/interface processes. 

Nonlinear Laser Spectroscopy and Dephasing of Molecules An Experimental and Theoretical Overview, M. J. Bums, W. K. Liu, and A. H. Zewail, in Spectroscopy and Excitation Dynamics of Condensed Molecular Systems, Series in Modem Problems in Condensed Matter Sciences, Vol. 4, V. M. Agranovich and R. M. Hochstrasser, Eds., North-Holland Publishing, Amsterdam, New York, Oxford, 1983, Chapter 7, p. 301. 

Figure 1. Experimental set-up for performing transient two-photon ionization spectroscopy on metal clusters. The particles were produced in a seeded beam expansion, their flux detected with a Langmuir-Taylor detector (LTD). The pump and probe laser pulses excited and ionized the beam particles. The photoions were size selectively recorded in a quadrupole mass spectrometer (QMS) and detected with a secondary electron multiplier (SEM). The signals were then recorded as a function of delay between pump and probe pulse.

Platinum porphyrin complexes can be prepared by reaction with PtCl2(PhCN)2. Purification of the final complex is by medium pressure liquid chromatography on alumina. The strongly phosphorescent platinum(II) porphyrin complexes are efficient sensitizers for stilbene isomerization. The quantum yields for the cis to trans process are greater than unity because of a quantum chain process in which the metalloporphyrin serves both as an energy donor and an acceptor.1110 Picosecond laser spectroscopy has been used to obtain time-resolved excited-state spectra of platinum octaethylporphyrin complexes, and to probe the excited-state energy levels.1111 Tetrabenzoporphyrin complexes have been prepared for platinum in both the divalent and tetravalent oxidation states. The divalent complex shows strong phosphorescence at 745 nm.1112... 

Laser spectroscopy of the 1S-2S transition has been performed by Mills and coworkers at Bell Laboratories (Chu, Mills and Hall, 1984 Fee et al, 1993a, b) following the first excitation of this transition by Chu and Mills (1982). Apart from various technicalities, the main difference between the 1984 and 1993 measurements was that in the latter a pulse created from a tuned 486 nm continuous-wave laser with a Fabry-Perot power build-up cavity, was used to excite the transition by two-photon Doppler-free absorption, followed by photoionization from the 2S level using an intense pulsed YAG laser doubled to 532 nm. Chu, Mills and Hall (1984), however, employed an intense pulsed 486 nm laser to photoionize the positronium directly by three-photon absorption from the ground state in tuning through the resonance. For reasons outlined by Fee et al. (1993b), it was hoped that the use of a continuous-wave laser to excite the transition would lead to a more accurate determination of the frequency interval than the value 1233 607 218.9 10.7 MHz obtained in the pulsed 486 nm laser experiment (after correction by Danzmann, Fee and Chu, 1989, and adjustment consequent on a recalibration of the Te2 reference line by McIntyre and Hansch, 1986). 

The key development for using probe ions to study mineral systems is site selective laser spectroscopy. A tunable dye laser is tuned to match the absorption line of a particular ion with a particular environment or site within the sample. Only that ion will be excited and only that ion will fluoresce so the resulting fluorescence spectrum is much simpler than the conventionally obtained spectrum. 

Kochi et al. [111-113] have utilized time-resolved laser spectroscopy to examine the excited complexes. For the indene (IN)/TCNE system, excitation of the CT complex (532 nm) afforded not only absorption bands assigned to TCNE anion radical and IN cation radical, but also an absorption band due to an unidentified intermediate. Kochi proposed a 1,4-diradical or 1,4-zwitterionic intermediate, and postulated bond-formation as follows [111] ... 

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