Breakdown of the spectator model for the OH bonds in studying the H+H2O reaction

The time-dependent wave packet method is used to study the exchange and abstraction processes for the H+H2O reaction with both OH bonds in the H2O reactant treated as reactive bonds in full dimension. The calculation clearly shows that it is necessary to treat both OH bonds in this way in order to accurately investigate the exchange process. However, for the abstraction process, the spectator model works very well. Nonreactive treatment of one OH bond by using a few vibrational basis functions or even freezing the bond can yield very accurate abstraction reaction probability.     

Insertion and abstraction pathways in the reaction O(1D2) + H2-->OH+H

Rigorous quantum dynamical calculations have been performed on the ground 1 1A' and first excited 1 1A" electronic states of the title reaction, employing the most accurate potential energy surfaces available. Product rovibrational quantum state populations and rotational angular momentum alignment parameters are reported, and are compared with new experimental, and quasiclassical trajectory calculated results. The quantum calculations agree quantitatively with experiment, and reveal unequivocally that the 1 1A" excited state participates in the reaction.     

Effect of a single quantum rotational excitation on state-to-state dynamics of the O(1D)+H2-->OH+H reaction

Crossed molecular beams scattering experiments on the O(1D)+H2 reaction have been carried out in order to study the effect of the reagent (H2) rotational excitation on the detailed dynamics of this benchmark insertion reation. Experimental results indicate that a single quantum rotational excitation of H2 has a significant impact on the product state distributions at the forward and backward scattering directions, while very little effect has been found in the sideway scattering direction. No clear patterns of this effect are found in the OH-product state distributions, indicating that the single quantum excitation on the dynamics is rather complicated.     

Cross section for the H+H2O abstraction reaction: experiment and theory

The absolute value of the cross section for the abstraction reaction between fast H atoms and H2O has been determined experimentally at a mean collision energy of 2.46 eV. The OH population distribution at the same mean energy has also been determined. The new measurements are compared with state-of-the-art quantum mechanical and quasiclassical scattering calculations on the most recently developed potential energy surface.     

State to state to state dynamics of the D+H2 -->HD+H reaction: control of transition-state pathways via reagent orientation

The influence of reagent rotation on the dynamics of the D+H2 -->HD+H reaction is studied. The state-resolved differential cross section is measured using the Rydberg-atom scheme in a crossed beam experiment. It is found that the H2 rotation has a strong influence on the results. This effect was traced to the selection of the quantum bottleneck states through reagent orientation, thus suggesting a novel strategy to control the transition-state pathways in direct chemical reactions.     

Simultaneous single-shot imaging of OH and O2 using a two-wavelength excimer laser

A technique is described for simultaneous single-shot imaging of OH and O₂. Laser-induced fluorescence of both molecules is excited by a tunable KrF laser, which is operated simultaneously on two wavelengths. By using two CCD detectors with image intensifiers and suitable filters, separate images of OH and O₂ distributions in H₂/O₂ and hydrocarbon/air flames were obtained.     

Theoretical study on collision dynamics of H+ + H2O at low energies

Scattering dynamics of a water molecule in collision with proton is studied based on a time-dependent density functional theory and coupled with the molecular dynamics method, in which the electrons are described by quantum mechanics and the nuclei are described by classical mechanics. Four different incident directions at 46 eV are chosen in order to investigate the orientations effect, and the energy-dependent effect in low energy region is explored under impact energies 27, 36 and 46 eV. Reaction channels, scattering angles and energy loss of protons are calculated. The differences between those characteristics are unobvious in large impact parameters, which are irrespective of the incident orientations due to weak projectile-target interaction. In small impact parameters, the results strongly depend on the collision energy and orientation.     

Rotational distribution of nascent OH radicals after H2O2 photolysis at 193 nm

The rotational distribution of OH(X ²,v=0) radicals was investigated by resonant laser-induced fluorescence (LIF) after photolysis of H₂O₂ at 193 nm. A microcomputer equipped LIF arrangement allowed special shot-by-shot normalization of the fluorescence signal for noise reduction. Using a least-squares procedure we were able to account for all measured line intensities including overlapping lines (blends) and obtain a complete rotational state distribution of the OH(X ²,v=0) state. The rotational excitation shows a Gaussian-like distribution with a maximum atK=12 and with 16% of the total available energy (17,400 cm^–1) appearing in rotation. Only 1% of the available energy is converted into vibration, leaving over 83% for translational excitation. The measured rotational distribution appears to fit a semiclassical theory.     

Two-photon predissociative fluorescence of H2O by a KrF laser for concentration and temperature measurement in flames

Two-photon laser-induced predissociative fluorescence (LIPF) of H₂O is examined as a potential measurement technique of H₂O concentration and temperature in flames. Two-photons of 248 nm light from a narrowband KrF laser excite H₂O to the highly predissociative state in a hydrogen-air flame. The subsequent bound-free emission is observed from 400–500 nm in the flame at temperatures of 1000–2000 K and is found to be free of fluorescence interference from other flame species. This LIPF signal is not affected by collisional quenching due to the short lifetime of the predissociative state (2.5 ps). Broadband laser dispersion spectra, narrowband laser dispersion spectra, laser excitation spectra and probability density functions of the H₂O fluorescence are obtained in the hydrogen flame. The H₂O LIPF signal is found to be temperature sensitive and a two-line LIPF technique is needed for concentration and temperature measurement. The accuracy of a two-line LIPF technique for H₂O concentration and temperature measurement is determined.     

Efficiencies of third bodies in the reaction H + O2 + M = HO2 + M

Vibrational transition probabilities have been calculated by the Schwartz, Slawsky and Herzfeld method [3] for the deactivation of HO₂* in collision with H₂, O₂ and CO₂. The relative efficiencies of H₂, O₂ and CO₂ are compared with their third-body efficiencies found experimentally and it is concluded that the transfer of large vibrational quanta from HO₂* is unlikely to play an important part in determining the position of the second explosion limit of the H₂/O₂ reaction. This conclusion is at variance with the explanation put forward by Walsh [1] of the ‘anomalous’ third-body efficiencies of H₂O and CO₂ in this reaction.     

Development of the reaction time accelerating molecular dynamics method for simulation of chemical reaction

We present a novel and efficient method to integrate chemical reactions into molecular dynamics to simulate chemical reaction systems. We have dubbed this method RTAMD, an acronym for reaction time accelerating molecular dynamics. The methodology we propose here requires no more than the knowledge of the empirical intermolecular potentials for the species at play as well as the elementary reaction path among them. Bond formation during the simulation is performed by changing the inter-atomic potentials from those of the non-bonded species to those of the bonded ones, and a reaction is deemed to occur by the distance separating the bond forming atoms. In this way the energy barrier for a reaction is no longer considered; the estimation of the reaction rate, however, is possible by introducing the principles of the transition state theory. The simplicity of the present scheme to simulate chemical reactions enables it to be used in large-scale MD simulations involving a large number of simultaneous chemical reactions and to evaluate kinetic parameters. In this paper, the basic theory of the method is presented and application to simple equiatomic reaction system where the reaction rates were estimated was illustrated.     

Hydrogen bonding in mixed OH+H2O overlayers on Pt(111)

The stability of OH on Pt(111) has been investigated to determine the role of hydrogen bonding in stabilizing the overlayer. We find that the optimal structure is a mixed (OH+H2O) phase, confirming recent density-functional theory predictions. The reaction O+3H(2)O forms a hexagonal (sqrt[3]xsqrt[3])R30 degrees -(OH+H2O) lattice with a weak (3x3) superstructure, caused by ordering of the hydrogen bonds. The mixed overlayer can accommodate a range of H(2)O/OH compositions but becomes less stable as the H2O content is reduced, causing defects in the hydrogen-bonding network that lift the (3 x 3) superstructure and destabilize the overlayer.     

Characterization of hydrophobic,oxidized porous silicon layer formed by anodic etching of n+-type silicon surface in a HF:C2H5OH:HCl:H2O2:H2O electrolyte for bio-application

Porous silicon (PS) has been prepared in the dark by anodic etching of n⁺-type (111) silicon substrate in a HF:HCl:C₂H₅OH:H₂O₂:H₂O electrolyte. The processed PS layer is characterized by means of photoluminescence (PL) spectroscopy, scanning electron microscope (SEM), water contact angle (CA) measurements, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and micro-Raman scattering. The CA of fresh PS layer is found to be ~142°. On aging at ambient conditions, the CA decreases gently to reach ~133° after 3 month, and then it is stabilized for a prolonged time of aging. The visible PL emission from the PS layer also exhibits a good stability against aging time. The FTIR and XPS measurements and analysis show that the stable aged PS layer has rather SiO₂-rich surface. The micro/nanostructure nature of the PS layer is revealed from SEM and micro-Raman results and correlated to CA results. Stable hydrophobic surface of oxidized PS layer is attractive for bio-applications. The efficiency of the produced PS layers as an entrapping template for specific immobilization of IgG2a antibody via physical absorption process is demonstrated.     

Interfacial reaction barriers during thin-film solid-state reactions: The crystallographic origin of kinetic barriers at the NiS2/Si(111) interface

Epitaxial NiSi₂ islands have been grown on Si(111) substrates by the direct reaction of nickel vapour with the silicon substrate in ultra-high vacuum at 400° C. Growth kinetics was shown to depend on the orientation of the islands: A-oriented islands grow about ten times faster than B-oriented ones, with the ratio of the advance rates of the main growth fronts even reaching 30. Applying plan-view transmission electron microscopy and high-resolution electron microscopy of cross sections, a corresponding difference was found in the structure of the NiSi₂/Si(111) growth front: Steps at the B-oriented growth front were of three or six interplanar (111) spacings in height, whereas at the A-oriented growth front step-like defects of less than one interplanar (111) spacing in height were observed. These observations are explained by an atomic-scale model of the solid-state reaction, which involves the diffusion of nickel to the interfaces and the nucleation and subsequent lateral propagation of interfacial steps. The difference in the reaction kinetics originates from the presence of kinetic reaction barriers at the NiSi₂/Si(111) growth fronts, the barrier at the B-front being higher owing to the lower formation rate of steps of triple atomic height than that of steps of lower height at the A-NiSi₂/Si(111) growth front.