Water vibrationally excited, from

An important area that has yet to be fully explored is the effect of the flexibility of water molecules. The intennolecular forces in water are large enough to cause significant distortions from the gas-phase monomer geometry. In addition, the flexibility is cmcial in any description of vibrational excitation in water. 

Color from Vibrations and Rotations. Vibrational excitation states occur in H2O molecules in water. The three fundamental frequencies occur in the infrared at more than 2500 nm, but combinations and overtones of these extend with very weak intensities just into the red end of the visible and cause the blue color of water and of ice when viewed in bulk (any green component present derives from algae, etc). This phenomenon is normally seen only in H2O, where the lightest atom H and very strong hydrogen bonding combine to move the fundamental vibrations closer to the visible than in any other material. 

The overall OD vibrational distribution from the HOD photodissociation resembles that from the D2O photodissociation. Similarly, the OH vibrational distribution from the HOD photodissociation is similar to that from the H2O photodissociation. There are, however, notable differences for the OD products from HOD and D2O, similarly for the OH products from HOD and H2O. It is also clear that rotational temperatures are all quite cold for all OH (OD) products. From the above experimental results, the branching ratio of the H and D product channels from the HOD photodissociation can be estimated, since the mixed sample of H2O and D2O with 1 1 ratio can quickly reach equilibrium with the exact ratios of H2O, HOD and D2O known to be 1 2 1. Because the absorption spectrum of H2O at 157nm is a broadband transition, we can reasonably assume that the absorption cross-sections are the same for the three water isotopomer molecules. It is also quite obvious that the quantum yield of these molecules at 157 nm excitation should be unity since the A1B surface is purely repulsive and is not coupled to any other electronic surfaces. From the above measurement of the H-atom products from the mixed sample, the ratio of the H-atom products from HOD and H2O is determined to be 1.27. If we assume the quantum yield for H2O at 157 is unity, the quantum yield for the H production should be 0.64 (i.e. 1.27 divided by 2) since the HOD concentration is twice that of H2O in the mixed sample. Similarly, from the above measurement of the D-atom product from the mixed sample, we can actually determine the ratio of the D-atom products from HOD and D2O to be 0.52. Using the same assumption that the quantum yield of the D2O photodissociation at 157 nm is unity, the quantum yield of the D-atom production from the HOD photodissociation at 157 nm is determined to be 0.26. Therefore the total quantum yield for the H and D products from HOD is 0.64 + 0.26 = 0.90. This is a little bit smaller ( 10%) than 1 since the total quantum yield of the H and D productions from the HOD photodissociation should be unity because no other dissociation channel is present for the HOD photodissociation other than the H and D atom elimination processes. There are a couple of sources of error, however, in this estimation (a) the assumption that the absorption cross-sections of all three water isotopomers at 157 nm are exactly the same, and (b) the accuracy of the volume mixture in the... 

Figure 3 Inelastic and elastic cross sections for electron impact excitation of the water molecule the data are from the review by Mark et al. [19]. The total interaction cross section ctt was determined from the sum of cross sections for all elastic and inelastic processes. Inelastic channels include the vibrational modes Cvi (the bending mode with threshold 0.198 eV), cTv2 (the sum of two stretching modes with thresholds 0.453 and 0.466 eV), and CvS (a lump sum of other vibrational excitation modes including higher hormonics and combinational modes with an assigned threshold of 1 eV). The electronic excitations and <7 2 have threshold energies of 7.5 and 13.3 eV. Ionization cross sections are those of Djuric et al. (O), and Bolarizadah and Rudd ( ). (From Ref 19.)...

In suggesting an increased effort on the experimental study of reaction rates, it is to be hoped that the systems studied will be those whose properties are rather better defined than many have been. By far and away more information is known about the rate of reactions of the solvated electron in various solvents from hydrocarbons to water. Yet of all reactants, few can be so poorly understood. The radius and solvent structure are certainly not well known, and even its energetics are imprecisely known. The mobility and importance of long-range electron transfer are not always well characterised, either. Iodine atom recombination is probably the next most frequently studied reaction. Not only are the excited states and electronic relaxation processes of iodine molecules complex [266, 293], but also the vibrational relaxation rate of vibrationally excited recombined iodine molecules may be at least as slow as the recombination rate [57], Again, the iodine atom recombination process is hardly ideal. 

Mixtures of ozone (4 to 6 mm. of Hg pressure) and ammonia, hydrogen, hydrogen chloride, methane, or water (up to 150 mm. of Hg pressure) were flashed (7). In each system the spectrum of the OH radical was observed in the 0,0 1,0 1,1 2,1 2,2 and 3,2 bands of the A2S+ — system. Transitions from vibrationally excited levels were visible for 15 jujsec. and those from the zeroth level for up to 75 /jisec. In addition, the spectra of NH, O2, and CIO were recorded, the latter persisting for 1 msec. The only spectrum visible after this time was that of formaldehyde. 

The results obtained from the irradiation at 235 nm of vibrationally excited dichloromethane suggest that there is higher non-adiabaticity for vibrationally excited molecules.Laser irradiation at 355 nm of methylene chloride and methylene bromide brings about ionization.A simple C-Br bond fission is the key step in the photodissociation of methylene dibromide at 248 nm. Ionization of methylene bromide in the 10-24 eV range has been reported. Irradiation of methylene iodide in water has provided evidence for the formation of iodine atoms and protons.Further work on the photochemical behaviour of methylene iodide has reported that vibrationally relaxed CH2l- T reacts with cyclohexene to afford norcarane. ... 

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