Photodissociation modeling

Heller E J 1978 Quantum corrections to classical photodissociation models J. Chem. Rhys. 68 2066... 

Strong parallels are observed between the reactions of Yb and alkaline earth metals with halomethanes [399]. The trends in the energy disposal of the YbX product accord well with the impulsive photodissociation model [Sect. 3.1.3(c)]. The product vibrational distributions of the YbX from Yb + RX, when plotted against fv, show a marked dependence on the identity of R and an insensitivity to the nature of X (for Br and I), the distributions shifting to higher fv in the sequence CH3, CH2X, CF3 (Fig. 12). 

Heller. E.J. (1978) Quantum corrections to clasical photodissociation models, J. Chern. Phys. 68, 2066-2075. 

E. J. Heller, Quantum corrections to classical photodissociation models, J. Chem. Phys. 68 2066 (1978) Photofragmentation of triatomic molecules, J. Chem. Phys. 68 3891 (1978). 

The simple difhision model of the cage effect again can be improved by taking effects of the local solvent structure, i.e. hydrodynamic repulsion, into account in the same way as discussed above for bimolecular reactions. The consequence is that the potential of mean force tends to favour escape at larger distances > 1,5R) more than it enliances caging at small distances, leading to larger overall photodissociation quantum yields [H6, 117]. 

Dardi P S and Dahler J S 1990 Microscopic models for iodine photodissociation quantum yields in dense fluids J. Chem. Phys. 93 242-56... 

Lin C Y and Dunbar R C 1994 Time-resolved photodissociation rates and kinetic modeling for unimolecular dissociations of iodotoluene ions J. Rhys. Chem. 98 1369-75... 

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]. 

The outcome of the polymerization depends strongly on the particular monomer. Polymerizations of S, MMA, MA, VAc and some derivatives have been reported. Studies on model compounds indicate that the primary or secondary dithiocarbamatc end groups arc much less susceptible to photodissociation than benzyl or tertiary derivatives. 

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. 

Figure 17. Internal energy distributions of HCO from photodissociation of CH2O at 2549 cm (upper panel) and 2627 cm (lower panel) above the threshold for the H + HCO channel. The HCO vibrational thresholds are labeled with their quantum numbers, and combs label the stack thresholds. The open circles show predictions of the SSE/PST model. The upper panel is indicative of an So dominant pathway. In the lower panel, T is dominant, but So structure can still be observed. Reprinted with permission from [51]. Copyright 2000, American Institute of Physics.

Figure 13. Phase lag between the photoionization and photodissociation of vinyl chloride resulting from the Gouy phase of the focused laser beam. The dashed curve shows the results of the analytical model discussed in the text, and the solid curve is a numerical calculation of the phase lag without adjustable parameters.

Photodissociation of the water molecule is a model system for both experimental and theoretical studies. Extensive experimental and theoretical studies have been performed on this system during the last few decades. Excitation in its longest wavelength ultraviolet absorption band around 150-200nm leads to the lowest excited singlet state Dissociation... 

The first question to ask about the formation of interstellar molecules is where the formation occurs. There are two possibilities the molecules are formed within the clouds themselves or they are formed elsewhere. As an alternative to local formation, one possibility is that the molecules are synthesized in the expanding envelopes of old stars, previously referred to as circumstellar clouds. Both molecules and dust particles are known to form in such objects, and molecular development is especially efficient in those objects that are carbon-rich (elemental C > elemental O) such as the well-studied source IRC+10216.12 Chemical models of carbon-rich envelopes show that acetylene is produced under high-temperature thermodynamic equilibrium conditions and that as the material cools and flows out of the star, a chemistry somewhat akin to an acetylene discharge takes place, perhaps even forming molecules as complex as PAHs.13,14 As to the contribution of such chemistry to the interstellar medium, however, all but the very large species will be photodissociated rapidly by the radiation field present in interstellar space once the molecules are blown out of the protective cocoon of the stellar envelope in which they are formed. Consequently, the material flowing out into space will consist mainly of atoms, dust particles, and possibly PAHs that are relatively immune to radiation because of their size and stability. It is therefore necessary for the observed interstellar molecules to be produced locally. 

In the simple steady-state model of Thaddeus,117 bare carbon cluster seed molecules with 12 carbon atoms are used with reaction 28 to produce large linear carbon clusters with sizeable abundances since it is assumed that the C +l ions produced in reaction 28 do not dissociate when they recombine with electrons if n >12. Rather, neutral Cn+1 clusters are formed which either photodissociate (slowly) or recombine further with C+. In this limited system, cluster growth would be catastrophic were it not for photodissociation. The large abundances of carbon clusters with 20 < n < 40 suggests that such molecules may well be the carriers of the well-known DIBs.118... 

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... 

Tetraethylthiuram disulfide (13) induces St polymerization by the photodissociation of its S-S bond to give the polymer with C-S bonds at both chain ends (15). The C-S bond further acts as a polymeric photoiniferter, resulting in living radical polymerization. Eventually, some di- or monosulfides, as well as 13, were also examined as photoiniferters and were found to induce polymerization via a living radical polymerization mechanism close to the model in Eq. (18), e.g., the polymerization of St with 35 and 36 [76,157]. These disulfides were used for block copolymer synthesis [75,157-161] ... 

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