Energy dependence of methanol proton transfer reaction rate
Methanol proton transfer reaction rate energy dependence
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Methanol proton transfer reaction rate energy dependence
Template catalysis of acetyl transfer reactions, showing triple helices formation by polyuridylic acid with adenoside derivatives
A model for outer-sphere bimolecular electron transfer reactions is presented which is based on a rate expression correct in the adiabatic, nonadiabatic, and intermediate dynamical regimes for an overdamped solvent coordinate. A complete discussion of the time-scale separations needed to define a bimolecular rate for these electron transfer reactions is given. Bimolecular reaction rates are predicted to display distinct solvent and electronic coupling dependencies, defined by a few experimentally variable parameters.
Charge-transfer reactions in collisions between highly charged ions and neutral atoms of hydrogen and/or helium may be rapid at thermal energies. If these reactions are rapid, they will suppress highly charged ions in H I regions and guarantee that the observed absorption features from such ions cannot originate in the interstellar gas. A discussion of such charge-transfer reactions is presented and compared with the available experimental data. The possible implications of these reactions for observations of the interstellar medium, H II regions, and planetary nebulae are outlined.
The charge transfer reactions: Xe(+) + O2 yields O2(+) + Xe and O2(+) + Xe yields Xe(+) + O2 were studied using photoionization mass spectroscopy. It is shown that the reaction of Xe(+)(2P-3/2) ions with O2 molecules is much more efficient than the reaction of Xe(+)(2P-1/2) ions with O2 molecules. The charge transfer reaction of O2(+) ions with Xe atoms was detected for O2(+) ions in the a 4Pi-u state.
Electron transfer reactions and formation of polyradicalanions
Ion cyclotron resonance methods were used to measure the product distributions for thermal-energy charge-transfer reactions of He(+), Ne(+), and Ar(+) ions with N2, O2, CO, NO, CO2, and N2O. Except for the He(+)-N2 reaction, no molecular ions were formed by thermal-energy charge transfer from He(+) and Ne(+) with these target molecules. The propensity for dissociative ionization channels in these highly exothermic charge-transfer reactions at thermal energies contrasts with the propensity for formation of parent molecular ions observed in photoionization experiments and in high-energy charge-transfer processes. This difference is explained in terms of more stringent requirements for energy resonance and favorable Franck-Condon factors at thermal ion velocities.
An investigation is conducted concerning the ionization equilibrium of carbon in a hot intercloud medium (ICM), taking into account various charge-transfer reactions. Attention is given to problems related to observations of carbon along the lines of sight to several unreddened stars. It is pointed out that the observed underabundance of C III and overabundance of C I can be consistent with the presence of a hot, partially ionized ICM, provided that two of the charge-transfer reactions considered are rapid at thermal energies.
Stereospecificity in hydrogen transfer reaction characteristic of 6-keto steroids studied by mass spectrometry
A model is presented for outer-sphere bimolecular electron-transfer reactions which is correct in the adiabatic, nonadiabatic, and intermediate dynamical regimes for an overdamped solvent coordinate. From this model, the conditions for the transfer to be adiabatic or nonadiabatic are deduced. The time-scale separations needed to adequately describe the process as an average over (distant dependent) unimolecular rates are described.
The concept of tunnelling in the theory of electron and proton transfer reactions has recently been questioned on the ground that the situation is a nonstationary one. It has been suggested that time-dependent perturbation theory should be applied to obtain the quantum mechanical transition probability. We have done this for a square barrier. The result for most reactions is the same as obtained by the WKB approximation.
A helium-nitrogen laser is described in which energy in the visible range is emitted as a result of charge transfer reaction between helium ions and nitrogen molecules. The helium and nitrogen are present in a gas mixture at several atmospheres pressure, with a nitrogen partial pressure on the order of a pair of main discharge electrodes, the gas mixture is preionized to prevent arcing when the discharge pulse is applied. The preionization is achieved by the application of a high voltage across a pair of secondary electrodes which are spaced apart in a direction perpendicular to the spacing direction of the main discharge electrodes and the longitudinal axis of the space in which the gas mixture is contained. Feedback, by means of a pair of appropriately spaced mirrors, is provided, to produce coherent energy pulses at a selected wavelength.
The design of a shift register memory at the molecular level is described in detail. The memory elements are based on a chain of electron-transfer molecules incorporated on a very large scale integrated (VLSI) substrate, and the information is shifted by photoinduced electron-transfer reactions. The design requirements for such a system are discussed, and several realistic strategies for synthesizing these systems are presented. The immediate advantage of such a hybrid molecular/VLSI device would arise from the possible information storage density. The prospect of considerable savings of energy per bit processed also exists. This molecular shift register memory element design solves the conceptual problems associated with integrating molecular size components with larger (micron) size features on a chip.
The rate constants for proton transfer from H3(+) ions to N2, O2, and CO have been measured as function of hydrogen-buffer-gas partial pressure. The rate constant for proton transfer from H3(+) to N2 shows a very large pressure dependence, increasing from 1.0 by 10 to the -9th power cu cm/s at low H2 partial pressures to 1.7 by 10 to the -9th power cu cm/s at high H2 partial pressures. The rate constants for proton transfer from H3(+) to O2 and CO are constant with partial pressure of H2. The roles of excess vibrational energy in H3(+) ions and of equilibrium between forward and back reactions are discussed. Back reaction is observed only for the reaction of H3(+) ions with O2, and an equilibrium constant of 2.0 (plus or minus 0.4) at 298 K has been determined. From these data, the proton affinity of O2 is deduced to be 0.47 (plus or minus 0.11) kcal/mole higher than that of H2.
Large deuterium isotope effect on fluorescence emission spectra and quantum yields observed in number of chromospheres that contain proton donor groups
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