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1.
This New Views article will highlight some recent advances in high sensitivity gas detection using direct infrared absorption frequency comb laser spectroscopy, with a focus on frequency comb use in chemical reaction kinetics and our own contribution to this field. Our recently implemented detection technique uses a combination of a 12.9?GHz free spectral range virtually imaged phased array and diffraction grating to spatially disperse the mid-infrared frequency comb onto a camera. Individual frequencies or ‘comb teeth’ of a 250?MHz repetition-rate frequency comb are able to be resolved. High molecular sensitivity is achieved by increasing the interaction path length using a Herriott multipass cell. High spectral resolution, broadband spectral coverage, and high molecular sensitivity are all achieved on an adjustable 1–50 µs timescale, making this frequency comb apparatus ideal for measuring chemical reaction kinetics where multiple absorbing species can be monitored simultaneously. This New Views article will also discuss some of the challenges and decisions that chemists might face in implementing this advanced physics technology in their own laboratory.

Spatially dispersed 250 MHz mid-infrared frequency comb laser, with absorption of some frequencies by a dilute sample of methane.  相似文献   

2.
Kinetic-energy spectra and angular distribution of projectile-like fragments have been measured in the reaction of 84 MeV 12C on 169Tm, using the surface barrier silicon-based ΔE-E telescopes. The fragments close to the projectile show typical spectra of quasi-elastic transfer reactions, which were found to be in agreement with the calculations based on the direct surface transfer reaction model. A significant cross-section of fast alpha-particles was found at forward angles, reminiscent of incomplete fusion reactions, which could be explained in terms of the direct surface transfer reaction model after taking into account the level density of continuum states in the heavy reaction product. The results have been explained in terms of the continuous evolution of the reaction mechanism as a function of the mass transfer. Received: 13 March 2002 / Accepted: 3 May 2002  相似文献   

3.
We describe the (α n μ)—(d t μ) continuum above and below thed+(t μ)1 s threshold using theR-matrix formalism. The continuum is explicitly constructed in an adiabatic approximation, and the asymptotic phase shifts and amplitudes in all channels are obtained. The energy eigenstates are used to compute the fusion reaction cross section for in-flightd+(t μ) fusion, and fusion reaction rates involving transitions from thed+(t μ)1 s continuum to be below threshold continuum states.  相似文献   

4.
ABSTRACT

In this paper, we extend the familiar continuum electrostatic model to incorporate finite-size effects in the solvation layer, by perturbing the usual macroscopic interface condition. The perturbation is based on the mean spherical approximation (MSA), to derive a multiscale solvation-layer interface condition (SLIC/MSA). We show that SLIC/MSA reproduces MSA predictions for Born ions in a variety of polar solvents, including water as well as other protic and aprotic solvents. Importantly, the SLIC/MSA model predicts not only solvation free energies accurately but also solvation entropies, which standard continuum electrostatic models fail to predict. The SLIC/MSA model depends only on the normal electric field at the dielectric boundary, similar to our recent development of a SLIC model for charge-sign hydration asymmetry, and the reformulation of the MSA as an effective boundary condition enables its straightforward application to complex molecules such as proteins, whereas traditionally it is primarily a bulk theory. This work also opens the possibility for other electrolyte models to be incorporated into fast implicit-solvent models of biomolecular electrostatics.  相似文献   

5.
A reduced dimensionality model is used to study the reaction OO O 3 ( X1A1 ) + O( 3 P ) by means of time-dependent and time-independent quantum-mechanical methods. State-selected probabilities and rate constants are obtained for the reactive process as well as for the inelastic collision in which the vibrationally excited oxygen loses one or more quanta. It is found that the experimentally observed jump in depletion rates above a critical value of v could be partially explained by the vibrational relaxation rather than reaction. Reaction only becomes important for relatively high translational energies and therefore the calculated rates are too small at the temperatures of interest. It is concluded, however, that the reaction saddle point region in the potential energy surface plays a crucial role in the enhancement of vibrational relaxation. Received: 3 February 1998 / Revised: 27 March 1998 / Accepted: 15 May 1998  相似文献   

6.
We summarize three of our recent results on diffusion-influenced reactions in solutions. All deal with the concentration dependence of the reaction rate when the reactants must first diffuse together before reaction can occur. When one species (the sink species) is not dilute, the rate cannot be obtained by solution of a pair diffusion equation; the correlations among the sinks for the diffusing species must be accounted for. First, we consider fluorescence quenching when the quenchers are not dilute. For charged quenchers and fluorophores we discuss how the solution dielectric constant and ionic strength can strongly influence the deviations from the linear Stern-Volmer behavior (the dilute sink result) which arise due to the sink correlations. Second, we consider heterogeneous catalysis where a reactive species is adsorbed onto a surface and must surface diffuse to reactive sites (the sinks). We find that surface diffusion can be an important factor contributing to the rate of reaction; especially when surface diffusion is rapid relative to the adsorption/desorption rate. Third, we discuss diffusion influenced reactions with sinks which are long ellipsoids. Dilute long ellipsoids provide a large rate enhancement relative to a spherical sink; we show that this rate enhancement survives when nondilute ellipsoids are considered.  相似文献   

7.
《Nuclear Physics A》1997,621(4):879-896
Excitation energy spectra and neutron decay of xenon have been measured in extreme forward angle scattering of 250A and 400A MeV 17O ions, using one quadrant of the CELSIUS storage ring as a magnetic spectrometer. The observed excitation energy spectrum, ranging from 12 to 36 MeV, has been compared with Coulomb cross section calculations. Neutron and missing energy spectra are compared with statistical decay calculations using the code CASCADE. In addition to statistical decay from giant resonances and other continuum excitations, a large fraction of forward peaked fast neutrons was observed throughout the entire excitation energy region. A possible reaction mechanism behind these fast neutrons is discussed.  相似文献   

8.
S.H. Lin 《Molecular physics》2013,111(5):953-955
We present a unified theory of diatomic molecules which reconciles bound state spectroscopy and atomic scattering theory. The total wave-function is expanded in a complete set of atomic channel states which is entirely equivalent to an expansion in Hund's case (e) electronic-rotational states. An analysis of the coupled radial, that is vibrational, functions places strong constraints on the asymptotic properties of the molecular wave-functions. These are presented in terms of the reactance K and scattering S matrices of atomic scattering theory which offers a uniform treatment for open channels (inelastic scattering and continuum spectroscopy), closed channels (bound state spectroscopy) and mixtures of both (predissociation). The normalization of the total wavefunction is derived and related to the asymptotic boundary conditions both for continuum and bound states.  相似文献   

9.
A laser heating technique for studying fast surface processes has been applied in an initial study to the thermal desorption of D2 from a polycrystalline tungsten sample. This technique is a means for measuring surface reactions at rates, concentrations, and temperatures that approach conditions of technical interest, but with the high degree of definition and control made possible with an ultrahigh vacuum apparatus. The method is analogous to the fast temperature jump method used for studying reactions in condensed phases, and can sort out elementary processes that have differing activation energies. The variation of total flux desorbed with maximum surface temperature reached and initial surface coverage serves, with the aid of a model kinetic rate expression, to determine the desorption rate parameters. It is shown that the desorption of D2 from W at rates of 5 × 107 monolayers/sec is governed by the same kinetics as obtained by extrapolating previous measurements made at a rate about 105 times slower. The surface is subjected to a sufficiently fast and large temperature rise to desorb surface atoms or molecules in a time short compared to the range of flight times to a mass spectrometer detector. In this way the velocity distribution of the desorbing species may be determined. This along with the surface temperature history gives additional information on the reaction rate model and also whether the species are emerging in translational thermal equilibrium with the surface. In the present experiments a significant number of desorbatedesorbate collisions occur. Corrections are made for the collision effects in the interpretation of the data. It is shown how modifications of the technique can be made to substantially eliminate these effects. The present conditions were laser pulse width of 3 × 10?8 sec and surface temperature rise of 300 to 3000 K.  相似文献   

10.
Abstract

The hydrolysis of thiazolium salts is studied under varying pressures between 0.1 and 85 MPa. Activation and reaction volumes are obtained for different reaction steps. The results confirm the reaction scheme, where the thiazolium cation forms a pseudobase by addition of an hydroxide ion. The pseudobase can be protonated or can form a ring-opened species, which can further be deprotonated.  相似文献   

11.
Abstract

Chemical kinetics is the study of the rates and mechanisms of chemical reactions and the factors that influence those rates and mechanisms. Ideally, one would like to obtain quantitative concentration vs. time data from which rate constants can be calculated and mechanisms deduced. In the absence of quantitative data, however, the sequence of chemical events can still be deduced, provided a technique exists for observing intermediate species.  相似文献   

12.
Shu Huang  Jaime Marian 《哲学杂志》2013,93(20):2562-2583
ABSTRACT

The asymmetry in diffusion dimensionality between self-interstitial atom (SIA) clusters and vacancies is a fundamental feature of irradiation damage in crystals, leading to a defect buildup imbalance that manifests itself as measurable dimensional and mechanical property changes. It is well known that, while vacancies and mobile vacancy clusters diffuse in a three-dimensional (3D) fashion, SIA clusters perform one-dimensional motion along mostly rectilinear trajectories. Despite this, a complete set of kinetic coefficients, including coagulation reaction rates and sink strengths, does not exist for 1D-moving objects. In this paper, we derive analytical expressions for these coefficients from continuum diffusion theory particularised to 1D motion. Moreover, we carry out kinetic Monte Carlo simulations of numerical replicas of the geometry of diffusing particles and sinks to validate the proposed solutions. Our simulations, which are conducted entirely independently from the analytical derivations, reveal excellent agreement with the proposed expressions, adding confidence to their validity. We compare the 1D and 3D cases and discuss their relevance for kinetic codes for damage accumulation calculations.  相似文献   

13.
A demonstration that boron–oxygen related degradation in boron‐doped Czochralski silicon could be caused by a single defect with two trap energy levels is presented. In this work, the same two‐level defect can describe the fast and slow lifetime decay with a capture cross‐section ratio of electrons and holes for the donor level of σn/σp = 19 ± 4. A model is proposed for the multi‐stage degradation involving a single defect, in which the product of the slow reaction is a reactant in the fast reaction. After thermal processing, a population of interstitial oxygen (Oi) exists in a certain state (the precursor state) that can rapidly form defects (fast degradation) and another population of Oi exists in a state that is required to undergo a slow transformation into the precursor state before defect formation can proceed (slow degradation). Kinetic modelling is able to adequately reproduce the multi‐stage degradation for experimental data. Dark annealing is also shown to impact the extent of ‘fast’ degradation. By decreasing the dark annealing time on pre‐degraded wafers, a more severe ‘fast’ degradation of the samples can be enabled during subsequent illumination, consistent with this theory. The paper then discusses possible candidates for the chemical species involved. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)  相似文献   

14.
孙棣华  彭光含 《中国物理 B》2009,18(9):3724-3735
In this paper, the viscous continuum traffic flow model for a single lane is extended to the traffic flow for two-lane freeways. The proposed model is a higher-order continuum model considering the coupling and lane changing effects of the vehicles on two adjacent lanes. It results from integrating the Taylor series expansion of the viscous continuum traffic flow model proposed by Ge (2006 Physica A 371 667) into the multi-lane model presented by Daganzo (1997 Transpn. Res. B 31 83). Our proposed model may be used to describe non-anisotropic behaviour because of lane changing in multi-lane traffic. A linear stability analysis is given and the neutral stability condition is obtained. Also, issues related to lane changing, shock waves and rarefaction waves, local clustering and phase transition are investigated through a simulation experiment. The simulation results show that the proposed model is capable of explaining some particular traffic phenomena commonly observable in real world traffic flow.  相似文献   

15.
Hongjiang Ren 《Molecular physics》2013,111(23):3663-3672
The mechanism of H abstraction reactions for Isoflurane with the OH radical was investigated using density functional theory and G3(MP2) duel theory methods. The geometrical structures of all the species were fully optimised at B3LYP/6-311++G** level of theory. Thermochemistry data were obtained by utilising the high accurate model chemistry method G3(MP2) combined with the standard statistical thermodynamic calculations. Gibbs free energies were used for the reaction channels analysis. All the reaction channels were confirmed throughout the intrinsic reaction coordinate analysis. The results show that two channels were obtained, which correspond to P(1) and P(2) with the respective activation barriers of 63.03 and 54.82 kJ/mol. The rate constants for the two channels over a wide temperature range of 298.15–2000 K were predicted and the calculated data are in agreement with the experimental one. The results show that P(2) is the dominant reaction channel under 800 K and above 800 K, it can be found that P(1) will be more preferable reaction channel.  相似文献   

16.
Sheehan and coworkers have claimed [D. P. Sheehan et al., Found. Phys. 30, 1227 (2000); 32, 441 (2002); D. P. Sheehan, in Quantum Limits to the Second Law, AIP Conference Proceedings 643 (American Institute of Physics, Melville, NY, 2002), p. 391] that a dilute gas trapped between an external shell and a gravitator can support a steady state in which energy flux by particles in one direction is balanced by energy flux by radiation in the opposite direction, and in which work can be extracted from an isothermal heat reservoir, thereby violating the second law of thermodynamics. In this paper, we identify a fundamental error in their simulation and analysis of their model system that vitiates their conclusions. We analyze a simpler, exactly soluble, three-dimensional model of a very dilute gas in a gravitational field between two thermal reservoirs, and show that their conclusions are not supported for the simple model. We show that their method of simulation, when applied to either the simple model or their more complex model under simpler conditions where the answers are known, leads to unphysical results. We also show that, when appropriate sampling is done, their model gives results in accord with the second law and detailed balance.  相似文献   

17.
The potential of long-range interaction between two dissimilar atoms, one of which is excited, drops as 1/R 2 with the distance for the Casimir-Polder limit of large distances in comparison with the wave-length of atom transitions (E.A. Power and T. Thirunamachandran, Phys. Rev. A 51, 3660 (1995)). It is shown that such a dependence, obtained with the help of perturbation technique, results in a divergence for the interaction potential between an excited atom and a medium of dilute gas. We develop a nonperturbative method based upon quantum Green’s functions (Yu. Sherkunov, Phys. Rev. A 72, 052703 (2005)) to calculate the interaction potential for an excited atom and a ground-state atom embedded in a dielectric medium, taking into account the absorption of photons in the dielectric medium. The exponential suppression of the interaction between the atoms is demonstrated. The force acting on an excited atom near the interface of dilute gas medium is calculated. The result is no more divergent. The force between gas media in Casimir-Polder regime is calculated as well. The text was submitted by the author in English.  相似文献   

18.
19.
The radical (CH3)2 COMu has been studied in pure (CH3)2 CO and in binary aqueous systems. The value of the muon-electron hyperfine coupling constant fell sharply from 25.4 MHz to ca 22.5 MHz on the addition of low concentration of water. It then fell gradually on going to dilute solutions in water. The coupling increased with increasing temperature as expected for a positive hyperfine interaction. The results are compared with esr data for (CH3)2 COH radicals, and the solvent dependence is considered in terms of hydrogen-bonding. The mechanism of formation of these radicals is discussed in the light of reaction rates. It is concluded that their precursor cannot be muonium.  相似文献   

20.
Ming-Der Su 《Molecular physics》2015,113(13-14):1590-1599
The mechanisms of the photochemical isomerisation reactions are investigated theoretically using the model systems, 1,2-dihydro-1,2-phosphaborine (5) and 1,2-dihydro-1,2-alumazaine (6), using the CAS(6,6)/6-311G(d,p) and MP2-CAS-(6,6)/6-311++G(3df,3pd)//CAS(6,6)/6-311G(d,p) methods. For each model reactant, three reaction pathways, which lead to three kinds of photo-isomers, are examined. The structures of the conical intersections, which play a key role in such photo-rearrangements, are determined. The thermal (or dark) reactions of the reactant species are also examined, using the same level of theory, to provide a qualitative explanation of the reaction pathways. These model investigations demonstrate that the preferred reaction route for these two aromatic heterocyclics is as follows: reactant → Franck–Condon region → conical intersection → photoproduct. The theoretical evidences anticipate that after irradiation of 5, the photoproduct yield of the Dewar BP-isomer, 8, should be larger than that of the Dewar BP-isomer, 7, whereas no Dewar BP-isomer 9 can be observed. Moreover, the present theoretical data predict after irradiation of 6, all three Dewar AlN-isomers (10, 11, and 12) and the starting molecule, 6, are produced.  相似文献   

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