Electron Resonance of Vibrationally Excited OH Radicals

1971 ◽  
Vol 49 (17) ◽  
pp. 2207-2210 ◽  
Author(s):  
K. P. Lee ◽  
W. G. Tam ◽  
R. Larouche ◽  
G. A. Woonton

Hydroxyl radicals in the vibrational levels ν = 1, 2, 3, and 4 of 2Π3/2, J = 3/2 state were observed by means of electron resonance at a frequency of 8.9 GHz. The lambda doubling frequencies, the g factors, and the hyperfine interaction constants are obtained and they are in agreement with the results of another recent experiment.

1994 ◽  
Vol 72 (3) ◽  
pp. 673-677 ◽  
Author(s):  
Eric E. Aubanel ◽  
André D. Bandrauk

We examine two consequences of the unique behaviour of molecules in strong fields. First, by time gating of laser-induced avoided crossings with femtosecond laser pulses, one can obtain efficient vibrational inversion into a narrow distribution of vibrational levels of a molecular ion. We demonstrate this by numerical solution of the time-dependent Schrödinger equation for [Formula: see text] Second, we show results of numerical calculation with vibrationally excited [Formula: see text] of harmonic generation up to the 11th order of an intense 1064- nm laser. We predict that competition of photodissociation can be minimized by trapping the molecule in high-field-induced potential wells, thus enhancing the high-order harmonic generation process. Furthermore, the harmonic spectrum can serve as a measure of the structure of these laser-induced potentials.


1979 ◽  
Vol 57 (5) ◽  
pp. 619-634 ◽  
Author(s):  
J. A. Coxon ◽  
K. V. L. N. Sastry ◽  
J. A. Austin ◽  
D. H. Levy

The microwave absorption spectrum of the OH X2Π radical has been observed in all vibrational levels up to ν = 6. Experimental details are described of the tunable cavity and parallel plate Stark-modulated spectrometers employed for transitions below and above 23 GHz, respectively. The observed line frequencies, together with those reported by other workers, have been fitted using a non-linear least-squares routine with numerical diagonalization of the Hamiltonian matrix. Pseudo high-order corrections for centrifugal distortion of the Λ-doubling are required for the ν = 0 data, which now extend to J = 19/2 in the 2Π1/2 component. The various adjustable parameters of the Hamiltonian are compared with those of other similar models. The Λ-doubling and magnetic hyperfine constants for the different vibrational levels are reported, and several line frequencies of potential astrophysical significance are predicted.


1997 ◽  
Vol 15 (8) ◽  
pp. 984-998 ◽  
Author(s):  
A. V. Pavlov

Abstract. This study compares the OV1-10 satellite measurements of the integral airglow intensities at 630 nm in the SAR arc regions observed in the northern and southern hemisphere as a conjugate phenomenon, with the model results obtained using the time-dependent one-dimensional mathematical model of the Earth ionosphere and plasmasphere (the IZMIRAN model) during the geomagnetic storm of the period 15–17 February 1967. The major enhancements to the IZMIRAN model developed in this study are the inclusion of He+ ions (three major ions: O+, H+, and He+, and three ion temperatures), the updated photochemistry and energy balance equations for ions and electrons, the diffusion of NO+ and O2+ ions and O(1D) and the revised electron cooling rates arising from their collisions with unexcited N2, O2 molecules and N2 molecules at the first vibrational level. The updated model includes the option to use the models of the Boltzmann or non-Boltzmann distributions of vibrationally excited molecular nitrogen. Deviations from the Boltzmann distribution for the first five vibrational levels of N2 were calculated. The calculated distribution is highly non-Boltzmann at vibrational levels v > 2 and leads to a decrease in the calculated electron density and integral intensity at 630 nm in the northern and southern hemispheres in comparison with the electron density and integral intensity calculated using the Boltzmann vibrational distribution of N2. It is found that the intensity at 630 nm is very sensitive to the oxygen number densities. Good agreement between the modelled and measured intensities is obtained provided that at all altitudes of the southern hemisphere a reduction of about factor 1.35 in MSIS-86 atomic oxygen densities is included in the IZMIRAN model with the non-Boltzmann vibrational distribution of N2. The effect of using of the O(1D) diffusion results in the decrease of 4–6% in the calculated integral intensity of the northern hemisphere and 7–13% in the calculated integral intensity of the southern hemisphere. It is found that the modelled intensities of the southern hemisphere are more sensitive to the assumed values of the rate coefficients of O+(4S) ions with the vibrationally excited nitrogen molecules and quenching of O+(2D) by atomic oxygen than the modelled intensities of the northern hemisphere.


2021 ◽  
Author(s):  
Qinjian Li ◽  
Fei Xie ◽  
Yang Yi ◽  
Pengxiang Zhao ◽  
Xin Zhang ◽  
...  

AbstractSince Ohsawa et al. reported a biological antioxidant function of hydrogen in 2007, researchers have now shown it to exert protective effects in a wide range of human and animal disease models. Clinical observations and scientific arguments suggest that a selective scavenging property of H2 cannot adequately explain the beneficial effects of hydrogen. However, there is no experiment challenging the original published data, which suggested that molecular hydrogen dissolved in solution reacts with hydroxyl radicals in cell-free systems. Here we report that a hydrogen-saturated solution (0.6 mM) did not significantly reduce hydroxyl radicals in the Fenton system using 1 mM H2O2. We replicated the same condition as Ohsawa’s study (i.e. 5 μM H2O2), and observed a decrease in •OH radicals in both the H2-rich and N2-rich solutions, which may be caused by a decreased dissolved oxygen concentration. Finally, we determined the effect of hydrogen on a high-valence iron enzyme, horseradish peroxidase (HRP), and found that hydrogen could directly increase HRP activity in a dose-dependent manner. Overall, these results indicate that although H2 and •OH can react, the reaction rate is too low to have physiological function. The target of hydrogen is more complex, and its interaction with enzymes or other macro-molecules deserve more attention and in-depth study.


2007 ◽  
Vol 7 (3) ◽  
pp. 6803-6842 ◽  
Author(s):  
I. J. George ◽  
A. Vlasenko ◽  
J. G. Slowik ◽  
J. P. D. Abbatt

Abstract. The kinetics and reaction mechanism for the heterogeneous oxidation of saturated organic aerosols by gas-phase OH radicals were investigated under NOx-free conditions. The reaction of 150 nm diameter Bis(2-ethylhexyl) sebacate (BES) particles with OH was studied as a proxy for chemical aging of atmospheric aerosols containing saturated organic matter. An aerosol reactor flow tube combined with an Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS) and scanning mobility particle sizer (SMPS) was used to study this system. Hydroxyl radicals were produced by 254 nm photolysis of O3 in the presence of water vapour. The kinetics of the heterogeneous oxidation of the BES particles was studied by monitoring the loss of a mass fragment of BES with the ToF-AMS as a function of OH exposure. We measured an initial OH uptake coefficient of γ0 = 1.26 (±0.04), confirming that this reaction is highly efficient. The density of BES particles increased by up to 20% of the original BES particle density at the highest OH exposure studied, consistent with the particle becoming more oxidized. Electrospray ionization mass spectrometry analysis showed that the major particle-phase reaction products are multifunctional carbonyls and alcohols with higher molecular weights than the starting material. Volatilization of oxidation products accounted for a maximum of 17% decrease of the particle volume at the highest OH exposure studied. Tropospheric organic aerosols will become more oxidized from heterogeneous photochemical oxidation, which may affect not only their physical and chemical properties, but also their hygroscopicity and cloud nucleation activity.


2006 ◽  
Vol 24 (11) ◽  
pp. 2823-2839 ◽  
Author(s):  
V. A. Yankovsky ◽  
R. O. Manuilova

Abstract. The traditional kinetics of electronically excited products of O3 and O2 photolysis is supplemented with the processes of the energy transfer between electronically-vibrationally excited levels O2(a1Δg, v) and O2(b1Σ+g, v), excited atomic oxygen O(1D), and the O2 molecules in the ground electronic state O2(X3Σg−, v). In contrast to the previous models of kinetics of O2(a1Δg) and O2 (b1Σ+g), our model takes into consideration the following basic facts: first, photolysis of O3 and O2 and the processes of energy exchange between the metastable products of photolysis involve generation of oxygen molecules on highly excited vibrational levels in all considered electronic states – b1Σ+g, a1Δg and X3Σg−; second, the absorption of solar radiation not only leads to populating the electronic states on vibrational levels with vibrational quantum number v equal to 0 – O2(b1Σ+g, v=0) (at 762 nm) and O2(a1Δg, v=0) (at 1.27 µm), but also leads to populating the excited electronic–vibrational states O2(b1Σ+g, v=1) and O2(b1Σ+g, v=2) (at 689 nm and 629 nm). The proposed model allows one to calculate not only the vertical profiles of the O2(a1Δg, v=0) and O2(b1Σ


1998 ◽  
Vol 332 (2) ◽  
pp. 507-515 ◽  
Author(s):  
Stephen C. FRY

Scission of plant cell wall polysaccharides in vivo has generally been assumed to be enzymic. However, in the presence of l-ascorbate, such polysaccharides are shown to undergo non-enzymic scission under physiologically relevant conditions. Scission of xyloglucan by 1 mM ascorbate had a pH optimum of 4.5, and the maximum scission rate was reached after a 10–25-min delay. Catalase prevented the scission, whereas added H2O2 (0.1–10 mM) increased the scission rate and shortened the delay. Ascorbate caused detectable xyloglucan scission above approx. 5 µM. Dehydroascorbate was much less effective. Added Cu2+ (> 0.3 µM) also increased the rate of ascorbate-induced scission; EDTA was inhibitory. The rate of scission in the absence of added metals appeared to be attributable to the traces of Cu (2.8 mg·kg-1) present in the xyloglucan. Ascorbate-induced scission of xyloglucan was inhibited by radical scavengers; their effectiveness was proportional to their rate constants for reaction with hydroxyl radicals (•OH). It is proposed that ascorbate non-enzymically reduces O2 to H2O2, and Cu2+ to Cu+, and that H2O2 and Cu+ react to form •OH, which causes oxidative scission of polysaccharide chains. Evidence is reviewed to suggest that, in the wall of a living plant cell, Cu+ and H2O2 are formed by reactions involving ascorbate and its products, dehydroascorbate and oxalate. Systems may thus be in place to produce apoplastic •OH radicals in vivo. Although •OH radicals are often regarded as detrimental, they are so short-lived that they could act as site-specific oxidants targeted to play a useful role in loosening the cell wall, e.g. during cell expansion, fruit ripening and organ abscission.


1988 ◽  
Vol 8 (2-4) ◽  
pp. 123-135 ◽  
Author(s):  
A. V. Dem'Yanenko ◽  
G. A. Polyakov ◽  
A. A. Puretzky

We studied the IR luminescence spectra of vibrationally excited CF2Cl2 molecules resulting from excitation of the ν1 (1098 cm−1) and ν8 (922 cm−1) modes with a pulsed CO2 laser. The nonequilibrium spectra obtained under pumping conditions where their equilibrium counterparts coincide (the number of the photons absorbed per molecule being the same) were found to differ considerably. We suppose that this difference is due to different types of vibrational distribution formed as a result of the IR laser pumping. When pumping the ν1 mode, excitation of the R-branch occurs, resulting in the molecules “sticking” on the lower vibrational levels, whereas in the case of the ν8 mode, it is the P-branch that gets excited so that the molecules become easy to raise to high-lying vibrational levels.


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