Photodissociation of

Pack R T 1976 Simple theory of diffuse vibrational structure in continuous UV spectra of polyatomic molecules. I. Collinear photodissociation of symmetric triatomics J. Chem. Phys. 65 4765... 

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... 

There are many experimental methods by which photodissociation of ions have been studied. The earliest were crossed-beams experiments on Hjbeginning in the late 1960s [24, 25 and 26] and experiments on a... 

There has been much activity in the shidy of photodissociation of cluster ions, dating back to the 1970s when it was realized that most ions in the earth s lower atmosphere were heavily clustered [7, 35, 36],... 

Miller T M 1981 Photodetachment and photodissociation of ions Advances In Electronics and Electron Physics ed L Marten and C Marton (New York Academic)... 

Schwarzer D, Schroeder J and Schroder Ch 2000 Quantum yields for the photodissociation of iodine in compressed liquids and supercritical fluids Z. Phys. Chem. 214... 

Murrell J N, Stace A J and Dammel R 1978 Computer simulation of the cage effect in the photodissociation of iodine J. Chem. Soc. Faraday Trans. II 74 1532... 

Dardi P S and Dahler J S 1993 A model for nonadiabatic coupling in the photodissociation of l2-solvent complexes J. Chem. Phys. 98 363-72... 

Gezelter J D and Miller W H 1996 Dynamics of the photodissociation of triplet ketene J. Chem. Phys. 104 3546-54... 

FIdthmann H, Beck C, Schinke R, Woywod C and Domcke W 1997 Photodissociation of ozone in the Chappuis band. II. Time-dependent wave packet calculations and interpretation of diffuse vibrational... 

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... 

The experiments were perfonued in a static reaction cell in a large excess of N2 (2-200 bar). An UV laser pulse (193 mu, 20 ns) started the reaction by the photodissociation of N2O to fonu O atoms in the presence of NO. The reaction was monitored via the NO2 absorption at 405 mu using a Hg-Xe high-pressure arc lamp, together with direct time-dependent detection. With a 20-200-fold excess of NO, the fonuation of NO2 followed a pseudo-first-order rate law ... 

Figure B2.5.10. LIF signal of free Na atoms produced in the photodissociation of Nal. t - q is the delay between the photolysis pulse (at L) and the probe pulse. Adapted from [111].

Schinke R, Weide K, Heumann B and Engel V 1991 Diffuse structures and periodic orbits in the photodissociation of small polyatomic molecules Faraday Discuss. Chem. Soc. 91 31... 

Transient, or time-resolved, techniques measure tire response of a substance after a rapid perturbation. A swift kick can be provided by any means tliat suddenly moves tire system away from equilibrium—a change in reactant concentration, for instance, or tire photodissociation of a chemical bond. Kinetic properties such as rate constants and amplitudes of chemical reactions or transfonnations of physical state taking place in a material are tlien detennined by measuring tire time course of relaxation to some, possibly new, equilibrium state. Detennining how tire kinetic rate constants vary witli temperature can further yield infonnation about tire tliennodynamic properties (activation entlialpies and entropies) of transition states, tire exceedingly ephemeral species tliat he between reactants, intennediates and products in a chemical reaction. 

Photodissociation of a linear triatomic such as [85, 86] or Hgl2 [8] to produce a vibrationally excited diatomic, or cage recombination of a photodissociated diatomic such as I2 [78, 81] are classic model simple systems for reaction dynamics. Here we discuss tire Hgl2—>HgI + I reaction studied by Hochstrasser and co-workers [87, 88 and 89]. 

Figure C3.5.7. Possible modes of vibrational wavepacket (smootli Gaussian curve) motion for a highly vibrationally excited diatomic molecule produced by photodissociation of a linear triatomic such as Hglj, from [8].

Figure 3, Wavepacket dynamics of the photodissociation of NOCl, shown as snapshots of the density (wavepacket amplitude squared) at various times, The coordinates, in au, are described in Figure b, and the wavepacket is initially the ground-state vibronic wave function vertically excited onto the 5i state. Increasing corresponds to chlorine dissociation. The density has been integrated over the angular coordinate. The 5i PES is ploted for the geometry, 9 = 127, the ground-state equilibrium value,...

Certain, Y, Y-dialkyl dithioearbamates [e,g. benzyl A)/V-diethyl dithiocarbamate (14)] and xanthates have been used as photoinitiators. Photodissociation of the C-S bond of these compounds yields a reactive alkyl radical (to initiate polymerization) and a less reactive sulfur-centered radical (to undergo primary-radical termination) as shown in Scheme 9.9.30 41 4 ... 

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. 

Fig. 15. The optical spectrum of Cu Ar = 1 10 at 10-12 K, (A) showing isolated Cu atoms and Cuj molecules (B), (C) photoaggregation as the result of two 30-min irradiations in the resonance lines of Cu atoms at 302 nm, (D) photodissociation of Cu, resulting from a 30-min irradiation at the 370-nm band of Cu,. The features marked "a are thought to arise from secondary trapping sites of Cu,. Note the scale change between 325 and 400 nm (150).

Reactions with molecular species above the arrow e.g. RIO) involve subsequent reactions with these species to produce the indicated products. In most cases the reactants shown to the left of the arrow participate in the slowest or rate-determining step]. The CH3O radical formed in Rll then follows reaction R7. The H02 radical formed in RIO is the other member of the family and is linked with HO in a variety of chain reactions. These radicals are produced following HO attack on hydrocarbons or by photodissociation of oxygenated hydrocarbons such as formaldehyde (RIO) and acetaldehyde ... 

Uncertainties in Photochemical Models. The ability of photochemical models to accurately predict HO concentrations is undoubtedly more reliable in clean vs. polluted air, since the number of processes that affect [HO ] and [H02 ] is much greater in the presence of NMHC. Logan et al (58) have obtained simplified equations for [HO ] and [HO2 ] for conditions where NMHC chemistry can be ignored. The equation for HO concentration is given in Equation E6. The first term in the numerator refers to the fraction of excited oxygen atoms formed in R1 that react to form HO J refers to the photodissociation of hydrogen peroxide to form 2 HO molecules other rate constants refer to numbered reactions above. 

Here, X may be H, OH, NO, Cl, or Br. Cl from the photodissociation of chlorofluoro-carbons such as CFC-12 (CCI2F2) is the main known catalyst currently acting in the so-called... 

Photodissociation of Diiodoethane Hydrodynamics of Laser-Heated Liquids Gold Nanoparticles in Water... 

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