Light photodissociation

Heterogeneous photochemical reactions fall in the general category of photochemistry—often specific adsorbate excited states are involved (see, e.g.. Ref. 318.) Photodissociation processes may lead to reactive radical or other species electronic excited states may be produced that have their own chemistry so that there is specificity of reaction. The term photocatalysis has been used but can be stigmatized as an oxymoron light cannot be a catalyst—it is not recovered unchanged. 

The temi action spectroscopy refers to how a particular action , or process, depends on photon energy. For example, the photodissociation of 0 with UV light leads to energetic 0+0 fragments the kinetic energy released has been... 

Ozenne J-B, Pham D and Durup J 1972 Photodissociation ofH by monochromatic light with energy analysis of the e]ected H" ions Chem. Phys. Lett. 17 422-4... 

Flowever, in order to deliver on its promise and maximize its impact on the broader field of chemistry, the methodology of reaction dynamics must be extended toward more complex reactions involving polyatomic molecules and radicals for which even the primary products may not be known. There certainly have been examples of this notably the crossed molecular beams work by Lee [59] on the reactions of O atoms with a series of hydrocarbons. In such cases the spectroscopy of the products is often too complicated to investigate using laser-based techniques, but the recent marriage of intense syncluotron radiation light sources with state-of-the-art scattering instruments holds considerable promise for the elucidation of the bimolecular and photodissociation dynamics of these more complex species. 

Bardeen C J, Che J, WIson K R, Yakovlev V V, Cong P, Kohler B, Krause J L and Messina M 1997 Quantum control of Nal photodissociation reaction product states by ultrafast tailored light pulses J. Phys. Chem. A 101 3815-22... 

The absorption of a light pulse instantaneously generates reactive species in high concentrations, either tlirough the fomiation of excited species or tlirough photodissociation of suitable precursors. The reaction can... 

Irradiation of the molecular radical anion of DESO, which has a yellow color, with light of X = 350-400 nm partially restores the red color and the ESR spectrum of the radical-anion pair. Similarly to the case of DMSO-d6 a comparison of the energetics of the photodissociation of the radical anion and dissociative capture of an electron by a DESO molecule permits an estimation of the energy of the hot electrons which form the radical-anion pair of DESO. This energy is equal to 2eV, similarly to DMSO-d6. The spin density on the ethyl radical in the radical-anion pair of DESO can be estimated from the decrease in hfs in comparison with the free radical to be 0.81, smaller than DMSO-d6. 

We use laser photofragment spectroscopy to study the vibrational and electronic spectroscopy of ions. Our photofragment spectrometer is shown schematically in Eig. 2. Ions are formed by laser ablation of a metal rod, followed by ion molecule reactions, cool in a supersonic expansion and are accelerated into a dual TOE mass spectrometer. When they reach the reflectron, the mass-selected ions of interest are irradiated using one or more lasers operating in the infrared (IR), visible, or UV. Ions that absorb light can photodissociate, producing fragment ions that are mass analyzed and detected. Each of these steps will be discussed in more detail below, with particular emphasis on the ions of interest. 

S.3.4.3. Photodissociation It is also possible to use light as the activation method. Laser sources are especially useful because of their high intensity and narrow wavelength bandwidth. Photodissociation can be used to determine bond dissociation energies in ions directly, similar to what is done with threshold CID, or, alternatively, can be used in conjunction with direct ionization. 

Table 1. Vibrational populations of 02(1AS) from the photodissociation of ozone with light of wavelength A.

However, a shortcoming with the VUV photoionization approach is that absolute PI cross-sections are very often not known, and therefore branching ratios cannot be estimated. As matter of fact, studies of photodissociation processes by soft PI using synchrotron light are usually accompanied by measurements carried out using classic (hard) El ionization, where much data have to be taken at all possible fragment masses in order to estimate branching ratios.14-16,20... 

Fig. 30. Contour plot of photoelectron-photodissociation coincidence spectrum as a distribution of photoelectron intensity (dark shade = low, light shade = high) against the electron binding energy and relative translational energy of the photofragments. Also shown on the left and at the bottom are the partially averaged distributions for the translational energy release and the electron binding energy, respectively.

We have undertaken a gas phase photodissociation study of Mo2 2 H3 4 whose results are viewed in light of the one electron electronic structure models available for this compound... 

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