Water electronic excitation

At its best, the study of solvent kies by the formalism given can be used to learn about proton content and activation in the transition state. For this reason it is known as the proton inventory technique. The kinetics of decay of the lowest-energy electronic excited state of 7-azaindole illustrates the technique.25 Laser flash photolysis techniques (Section 11.6) were used to evaluate the rate constant for this very fast reaction. From the results it was suggested that, in alcohol, a double-proton tautomerism was mediated by a single molecule of solvent such that only two protons are involved in the transition state. In water, on the other hand, the excited state tautomerism is frustrated such that two water molecules may play separate roles. Diagrams for possible transition states that can be suggested from the data are shown, where of course any of the H s might be D s. 

We conclude with a consideration of a few other cobalt self-exchange reactions. The reaction in Eq. (9.33) is faster than that involving the ammine complexes (Eq. 9.30) because the water is a weaker-field ligand than ammonia. Thus, the activation energy for the formation of the electronically excited states is lower, as is the change in Co-ligand distances in the two oxidation states. 

Figure 7-11 and its caption (Crutzen, 1983) depict the most important of the gas phase and photochemical reactions in the atmosphere. Perhaps the single most important interaction involves the hydroxyl free radical, OH-. This extremely reactive radical is produced principally from the reactions of electronically excited atomic oxygen, 0( D), with water vapor. Photo-... 

D) is an electronically excited oxygen atom. It can decay back to a ground state oxygen atom ( P) (which will regenerate an ozone molecule), or else it can react with water to produce two OH radicals ... 

Photolysis of O3 yields O2 and electronically excited 0( D), which can either be collisionally stabilized (reaction 6.18) or react with a water molecule to yield two hydroxyl radicals (reaction 6.19). Atmospheric concentrations of hydroxyl radical on a 24-h seasonal average basis are estimated at 1 X 10 molecules cm while peak daytime concentrations of 46 X 10 molecules cm have been observed. ... 

Photolysis reactions often are associated with oxidation because the latter category of reactions frequently can be initiated by light. The photooxidation of phenothiazines with the formation of N- and S-oxides is typical. But photolysis reactions are not restricted to oxidation. In the case of sodium nitroprusside, it is believed that degradation results from loss of the nitro-ligand from the molecule, followed by electronic rearrangement and hydration. Photo-induced reactions are common in steroids [36] an example is the formation of 2-benzoylcholestan-3-one following irradiation of cholest-2-en-3-ol benzoate. Photoadditions of water and of alcohols to the electronically excited state of steroids have also been observed [37],... 

Pecourt J-ML, Peon J, Kohler B (2000) Ultrafast internal conversion of electronically excited RNA and DNA nucleosides in water. J Am Chem Soc 122 9348... 

Marian CM, Schneidaer F, Kleinschmidt M, Tatchen J (2002) Electronic excitation and singlet-triplet coupling in uracil tatutomers and uracil-water complexes. Eur Phys J D 20 357... 

Sukhan has used PTAB cationic micelles to enhance the CL reaction of 4-diethylaminophthalohydrazide with oxygen and Co(II) in the presence of fluorescein as sensitizer [48], This enhancement is mainly due to electron-excited energy transfer from the donor (4-diethylaminophthalohydrazide) to the acceptor (fluorescein). The addition of fluorescein combined with the presence of PTAB reduces the detection limit of Co(II) by a factor of 6. The method was successfully applied in the determination of Co in tap water samples. 

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.)...

At the end of the physical stage, which is within about 10 sec of the passage of the ionizing particle through the liquid, the track made by the particle contains H20", subexcitation electrons e , and electronically excited water molecules H2O in small clusters called spurs. From about 10 to 10 sec, the following processes are thought to occur and comprise the physicochemical stage [9,10] ... 

There are no experimental data of excitation cross sections for proton and alpha particle impact for water. The proton cross sections were obtained by scaling of the electron excitation cross sections for high-energy protons >500 keV [201]. For the lower-energy regions, the semiempirical model developed by Miller and Green [202] was adopted, which is based on the electron impact excitation. They assumed an analytical function for each excited level of the form... 

The major source of OH in remote areas is the photolysis of O, to electronically excited O( D), followed by its reaction with water vapor ... 

Furthermore, because these reactions result in the effective removal of NOx from ozone production, by removing N02, the model also predicts that O, concentrations will decrease. Figure 7.17, for example, shows the model results for the ratio of O, (R0i) with the heterogeneous removal of N03 and N2Os included to that without these aerosol reactions. In some locations, the 03 concentrations are predicted to be as much as 30% lower than they would have been in the absence of the heterogeneous reactions. Because 03 is also the major OH source on a global scale, via its photolysis to electronically excited oxygen atoms, O( D), which react in part with gas-phase water, this also decreases the predicted OH levels. 

The solvation dynamics following charge-transfer electronic excitation of diatomic solutes immersed in a methanol-water mixture provides a direct window on the molecular changes occurring upon solvent substitution. The solvation response of the mixtures is separated into methanol and water contributions in order to elucidate the role played by each molecular species on the solvation dynamics. Significandy different responses for the two solutes are found and related to the fact that the solute with the smaller site diameters is a much better hydrogen (H)-bond acceptor than the larger diameter solute (Skaf and Ladanyi, 1996). 

For ultraviolet irradiations care is needed in choosing a solvent— water, alkanes and acetonitrile are transparent and often unreactive towards electronically excited substrates alcohols and ethers are transparent but are more likely to be reactive acetone and benzene are sometimes used even though they are not transparent to all relevant wavelengths. It may be necessary to find out by trial and error whether or not an otherwise suitable solvent interferes with the photochemical process. A similar approach can be taken to decide about the need to purge continuously with an inert gas to remove dissolved oxygen. 

One of the most characteristic types of ground-state reaction for alkenes is electrophilic addition, often involving a proton acid as addend or catalyst. In the excited state similar reactions can occur, with water, alcohols or carboxylic acids as commonly encountered addends. However, there is a variety of photochemical mechanisms according to the conditions or substrate used. In a few instances it is proposed that the electronically excited state is attacked directly by a proton from aqueous acid, for example when styrenes are converted to l-arylethanols (2.47 the rate constant for such attack is estimated to be eleven to fourteen orders of magnitude greater than that for attack on the ground state, and the orientation of addition is that expected on the basis of relativecarbonium ion stabilities (Markowni-kov addition). 

The photodynamics of electronically excited indole in water is investigated by UV-visible pump-probe spectroscopy with 80 fs time resolution and compared to the behavior in other solvents. In cyclohexane population transfer from the optically excited La to the Lb state happens within 7 ps. In ethanol ultrafast state reversal is observed, followed by population transfer from the Lb to the La state within 6 ps. In water ultrafast branching occurs between the fluorescing state and the charge-transfer-to-solvent state. Presolvated electrons, formed together with indole radicals within our time resolution, solvate on a timescale of 350 fs. 

---