High-Resolution Laser Spectroscopy

Another method of measuring the relative quantum yield of the radical decomposition process (eq. 22) was also devised recently (144). This involves HNO chemiluminescence photoexcitation spectroscopy. When an H atom recombines with an NO molecule, an electronically excited HN0 ( A A" ) is formed. Fluorescence emission from HNO occurs at 762 nm. The HNO chemiluminescence in a low-pressure 1 10 mixture of H2CO and NO is proportional to the H-atom quantum yield from the photolysis of H2CO. The photoexcited HNO (red) chemiluminescence excitation spectrum of a H2CO/NO mixture obtained with a tunable laser at high resolution is shown in Fig. 2 together with an absorption spectrum and a H2CO fluorescence (blue) excitation spectrum (237). The relevant reaction scheme is as follows ... 

A number of halogenomethanes have been subjected to other forms of molecular spectroscopy. High-resolution Stark spectra of several transitions of the V3 band of CH3F have been studied by means of a CO2 laser measurements of the hyperfine structure on certain rotational transitions in CH2F2 have been made using a molecular beam maser spectrometer the millimetre-wave spectrum of ground-state CDCla and the microwave spectrum of CD3I in excited vibrational states have also been observed. 

T.W Hansch Repetitively pulsed tunable dye laser for high resolution spectroscopy. Appl. Opt. 11, 895 (1972)... 

JA Harrison, M Zahedi, JW Nibler. Use of seeded Nd YAG lasers for high-resolution spectroscopy. Opt Lett 18 149-151, 1993. 

Numerous applications of SFR lasers to high-resolution infrared spectroscopy have demonstrated the capabilities of this tunable laser type regarding spectral resolution and achievable signal-to-noise ratio (Sect.6.6). 

See also Fourier Transformation and Sampling Theory FT-Raman Spectroscopy, Applications Gas Phase Applications of NMR Spectroscopy High Resolution IR Spectroscopy (Gas Phase), Applications Hydrogen Bonding and Other Physicochemical Interactions Studied By IR and Raman Spectroscopy Laboratory Information Management Systems (LIMS) Laser Spectroscopy Theory Light Sources and Optics Vibrational, Rotational and Raman Spectroscopy, Historical Perspective. 

Quack M 1993 Molecular quantum dynamics from high resolution spectroscopy and laser chemistry J. Mol. Struct. 292 171-95... 

Quack M 1992 Time dependent intramolecular quantum dynamics from high resolution spectroscopy and laser chemistry Time Dependent Quantum Molecular Dynamics Experiment and Theory. Proc. NATO ARW 019/92 (NATO ASI Ser. Vol 299) ed J Broeckhove and L Lathouwers (New York Plenum) pp 293-310... 

Nonnal spontaneous Raman scahering suffers from lack of frequency precision and thus good spectral subtractions are not possible. Another limitation to this technique is that high resolution experiments are often difficult to perfomi [39]. These shortcomings have been circumvented by the development of Fourier transfomi (FT) Raman spectroscopy [40]. FT Raman spectroscopy employs a long wavelength laser to achieve viable interferometry. 

Hepburn J W 1995 Generation of coherent vacuum ultraviolet radiation applications to high-resolution photoionization and photoelectron spectroscopy Laser Techniques in Chemistry vol 23, ed A B Myers and T R Rizzo (New York Wley) pp 149-83... 

Nesbitt D J 1994 High-resolution direct infrared laser absorption spectroscopy in slit supersonic jets intermolecular forces and unimolecular vibrational dynamics in clusters Ann. Rev. Phys. Chem. 45 367-99... 

Figure 5.17 shows the rotational Raman spectrum of N2 obtained with 476.5 nm radiation from an argon ion laser. From this spectrum a very accurate value for Bq of 1.857 672 0.000 027 cm has been obtained from which a value for the bond length tq of 1.099 985 0.000 010 A results. Such accuracy is typical of high-resolution rotational Raman spectroscopy. 

New to the fourth edition are the topics of laser detection and ranging (LIDAR), cavity ring-down spectroscopy, femtosecond lasers and femtosecond spectroscopy, and the use of laser-induced fluorescence excitation for stmctural investigations of much larger molecules than had been possible previously. This latter technique takes advantage of two experimental quantum leaps the development of very high resolution lasers in the visible and ultraviolet regions and of the supersonic molecular beam. 

K. M. Siegbahn (Uppsala) development of high-resolution electron spectroscopy. N. Bloembergen (Harvard) and A. L. Schawlow (Stanford) development of laser spectroscopy. 

The other vibrational spectroscopies, laser Raman and magic angle spinning NMR, have also been useful. Despite its low resolution, high resolution EELS has been usefiil in UHV work for assessment of surface cleanliness and for the identification of adsorbed species. 

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