Vacuum ultraviolet generation

This teclnhque can be used both to pennit the spectroscopic detection of molecules, such as H2 and HCl, whose first electronic transition lies in the vacuum ultraviolet spectral region, for which laser excitation is possible but inconvenient [ ], or molecules such as CH that do not fluoresce. With 2-photon excitation, the required wavelengdis are in the ultraviolet, conveniently generated by frequency-doubled dye lasers, rather than 1-photon excitation in the vacuum ultraviolet. Figure B2.3.17 displays 2 + 1 REMPI spectra of the HCl and DCl products, both in their v = 0 vibrational levels, from the Cl + (CHg) CD reaction [ ]. For some electronic states of HCl/DCl, both parent and fragment ions are produced, and the spectrum in figure B2.3.17 for the DCl product was recorded by monitoring mass 2 (D ions. In this case, both isotopomers (D Cl and D Cl) are detected. 

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... 

For ion TOF measurement a probe laser was used to ionize reaction products in the reaction zone. The (1 + F) resonance-enhanced multiphoton ionization (REMPI) method was adapted for H-atom detection. The necessary vacuum ultraviolet (VUV) radiation near 121.6 nm (for Lyman-a transition) can readily be generated by a frequency-tripling technique in a Kr cell.37 The sensitivity of this (1 +1 ) REMPI detection scheme is extremely high owing to the large absorption cross-section of Lyman-a transition,... 

The difference in energy between a /l, and X B, has been estimated to be in the range from about 0.1 to about 1 eV. See a recent review by Chu and Dahler (211). Very recently a value of 0.27 eV was obtained as an upper limit of this energy difference from the occurrence of the process CH2CO > CH2(a1 /4,) + CO at 3370 A (258a). It has been known for many years that chemical reactivities of X3B, and a /t, states are very different. The Cl, state reacts 3 orders of magnitude faster than the iBl with H2 and CHa [Braun et al. (143)]. Both states are generated by the photolysis of ketene or diazomethane. Methylene is also a primary product of hydrocarbon photolysis in the vacuum ultraviolet [Ausloos and Lias (49)]. 

Photochemical behavior of monosilanes has been investigated by mercury-sensitized photolysis (15-19), flash photolysis (20, 21), vacuum ultraviolet photolysis (22-27), and matrix photolysis (28-30). The first examples of the photolysis of permethylated polysilanes were published in 1970 (14). All of the cyclic and acyclic permethylpolysilanes with the exception of hexamethyldisilane readily undergo photolysis on irradiation with ultraviolet light to give shorter chain compounds with the concurrent generation of the divalent silicon intermediate, dimethylsilylene (8). 

Experimental lifetime measurements on free atoms and ions performed by using pulsed laser excitation in the ultraviolet and vacuum-ultraviolet spectral regions are presented. Different methods of laser pulse generation, atomization and light detection are described. A short summary of results obtained is also given. Future possibilities in determination of lifetimes and transition probabilities in the short wavelengths region are discussed. 

Spectra with higher resolution are now available. The development of new experimental techniques such as tunable, vacuum ultraviolet radiation, generated by gas-phase four-wave-mixing processes, permits the resolution of rotational structure. 

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