Spectroscopic studies, lead electronic transitions

Electrochemical reductions of CO2 at a number of metal electrodes have been reported [12, 65, 66]. CO has been identified as the principal product for Ag and Au electrodes in aqueous bicarbonate solutions at current densities of 5.5 mA cm [67]. Different mechanisms for the formation of CO on metal electrodes have been proposed. It has been demonstrated for Au electrodes that the rate of CO production is proportional to the partial pressure of CO2. This is similar to the results observed for the formation of CO2 adducts of homogeneous catalysts discussed earlier. There are also a number of spectroscopic studies of CO2 bound to metal surfaces [68-70], and the formation of strongly bound CO from CO2 on Pt electrodes [71]. These results are consistent with the mechanism proposed for the reduction of CO2 to CO by homogeneous complexes described earlier and shown in Sch. 2. Alternative mechanistic pathways for the formation of CO on metal electrodes have proposed the formation of M—COOH species by (1) insertion of CO2 into M—H bonds on the surface or (2) by outer-sphere electron transfer to CO2 followed by protonation to form a COOH radical and then adsorption of the neutral radical [12]. Certainly, protonation of adsorbed CO2 by a proton on the surface or in solution would be reasonable. However, insertion of CO2 into a surface hydride would seem unlikely based on precedents in homogeneous catalysis. CO2 insertion into transition metal hydrides complexes invariably leads to formation of formate complexes in which C—H bonds rather than O—H bonds have been formed, as discussed in the next section. 

From photoelectron spectroscopic studies it is apparent that a second ionization channel starts at 11.4eV in the case of benzene, i.e., at about 2.15 eV above the first ionization potential.219 The tail of the calculated spectrum will, therefore, be buried beneath the second ionization threshold. The second ionization threshold is indicated on Figure 30 by an arrow. Finally, there have been recent suggestions that there are two a ionization potentials, at 10.35 and 10.85 eV.220 If correct, excitation of these a-electrons would also lead to absorption intensity obscuring the contribution of transitions of the elg orbitals. 

Cold, trapped HD+-ions are ideal objects for direct spectroscopic tests of quantum-electrodynamics, relativistic corrections in molecules, or for determining fundamental constants such as the electron-proton mass ratio. It is also of interest for many applications since it has a dipole moment. The potential of localizing trapped ions in Coulomb crystals has been demonstrated recently with spectroscopic studies on HD+ ions with sub-MHz accuracy. The experiment has been performed with 150 HD+ ions which have been stored in a linear rf quadrupole trap and sympathetically cooled by 2000 laser-cooled Be+ ions. IR excitation of several rovibrational infrared transitions has been detected via selective photodissociation of the vibra-tionally excited ions. The resonant absorption of a 1.4/itm photon induces an overtone transition into the vibrational state v = A. The population of the V = A state so formed is probed via dissociation of the ion with a 266 nm photon leading to a loss of the ions from the trap. Due to different Franck-Condon factors, the absorption of the UV photon from the v = A level is orders of magnitude larger than that from v = 0. 

Chromoproteins are characterized by an electronic absorption band in the near-UV, visible or near-IR spectral range. These bands may arise from Jt Jt" transitions of prosthetic groups or from charge-transfer transitions of specifically bound transition metal ions. Thus, chromoproteins which may serve as electron transferring proteins, enzymes or photoreceptors, are particularly attractive systems to be studied by RR spectroscopy since an appropriate choice of the excitation wavelength readily leads to a selective enhancement of the Raman bands of the chromo-phoric site. Moreover, these chromophores generally constitute the active sites of these biomolecules so that RR spectroscopic studies are of utmost importance for elucidating structure-function relationships. 

Transition metal oxides, rare earth oxides and various metal complexes deposited on their surface are typical phases of DeNO catalysts that lead to redox properties. For each of these phases, complementary tools exist for a proper characterization of the metal coordination number, oxidation state or nuclearity. Among all the techniques such as EPR [80], UV-vis [81] and IR, Raman, transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS) and NMR, recently reviewed [82] for their application in the study of supported molecular metal complexes, Raman and IR spectroscopies are the only ones we will focus on. The major advantages offered by these spectroscopic techniques are that (1) they can detect XRD inactive amorphous surface metal oxide phases as well as crystalline nanophases and (2) they are able to collect information under various environmental conditions [83], We will describe their contributions to the study of both the support (oxide) and the deposited phase (metal complex). 

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