Simulation of volume polarization for the influence of solvation on chemical shielding

The effect of bulk dielectric solvation on chemical shielding at nitrogen in CH₃CN is studied with reaction field theory. A previous work has demonstrated the strong influence on this property from volume polarization, which describes that part of the reaction field arising from solute charge density penetrating outside its cavity. The essentially exact treatment of volume polarization used in that work is computationally demanding, and a more facile method for simulation of the volume polarization has recently been proposed. It is found in the present work that this simulation of the volume polarization yields results in excellent agreement with the essentially exact treatment of the strong volume polarization effects on nitrogen shielding in CH₃CN.Contribution to the Jacopo Tomasi Honorary Issue     

Thermodynamic Studies on Amino Acid Solvation in Aqueous Urea

The present paper discusses the behaviour of transfer free energy of some amino acids from water to 4M, 6M and 8M aqueous urea. Dissection of transfer free energy into cavity term, interaction term and electrical term reveals that cavity forming free energy of transfer ΔG⁰_t (cav) plays an important role in dictating actual interaction of amino acids in aqueous urea. Cavity forming free energy of transfer has been estimated by using Scaled Particle Theory (SPT).     

Rapid monitoring of intermediate states and mass balance of nitrogen during denitrification by means of cavity enhanced Raman multi-gas sensing

The comprehensive investigation of changes in N cycling has been challenging so far due to difficulties with measuring gases such as N₂ and N₂O simultaneously. In this study we introduce cavity enhanced Raman gas spectroscopy as a new analytical methodology for tracing the stepwise reduction of ¹⁵N-labelled nitrate by the denitrifying bacteria Pseudomonas stutzeri. The unique capabilities of Raman multi-gas analysis enabled real-time, continuous, and non-consumptive quantification of the relevant gases (¹⁴N₂, ¹⁴N₂O, O₂, and CO₂) and to trace the fate of ¹⁵N-labeled nitrate substrate (¹⁵N₂, ¹⁵N₂O) added to a P. stutzeri culture with one single measurement. Using this new methodology, we could quantify the kinetics of the formation and degradation for all gaseous compounds (educts and products) and thus study the reaction orders. The gas quantification was complemented with the analysis of nitrate and nitrite concentrations for the online monitoring of the total nitrogen element budget. The simultaneous quantification of all gases also enabled the contactless and sterile online acquisition of the pH changes in the P. stutzeri culture by the stoichiometry of the redox reactions during denitrification and the CO₂-bicarbonate equilibrium. Continuous pH monitoring – without the need to insert an electrode into solution – elucidated e.g. an increase in the slope of the pH value coinciding with an accumulation of nitrite, which in turn led to a temporary accumulation of N₂O, due to an inhibition of nitrous oxide reductase. Cavity enhanced Raman gas spectroscopy has a high potential for the assessment of denitrification processes and can contribute substantially to our understanding of nitrogen cycling in both natural and agricultural systems.     

Cavity Ring-Down Spectroscopy coupled with helium microwave-induced plasma for fluorine detection

Cavity Ring-Down Spectroscopy with a tunable diode laser has been used for the detection of fluorine at trace levels. A homemade experimental setup was constructed to accommodate the microwave-induced plasma glow discharge inside the optical cavity. The energy delivered by helium plasma discharge was successfully used not only for the dissociation of fluorine molecules but, more importantly, also for the excitation of fluorine atoms into their metastable level 3s⁴P_5/2. The absorption observed at the 3s⁴P_5/2–3p⁴D^o_7/2 transition (corresponding to a 685.603-nm atomic line) was used for fluorine atom detection. Good agreement between theoretical and measured absorption line shapes confirmed the selectivity of fluorine atomic absorption. We observed an absorption coefficient of 4 ? 10⁻⁶ cm⁻¹, corresponding to a detection of F(3s⁴P_5/2) atoms at about 1.5 ? 10⁶ atoms cm⁻³. These data demonstrate that we achieved a detection limit of 100 ng g⁻¹ under the conditions of our initial homemade experimental setup. However, the optimization of the system may lead to the improvement of the detection limit by approximately two orders of magnitude.     

Entanglement and teleportation via a chaotic system

The dynamics of an entangled state interacting with a single cavity mode is investigated in the presence of a random parameter. We show that the degree of entanglement decays with time and that the rate of decay is defined by features of a random parameter. Quantum teleportation through a dissipative channel and teleportation fidelity as a function of damping rates have been studied. The sensitivity of the fidelity with respect to the random parameter is discussed. We have evaluated the time interval during which one can perform quantum teleportation and send the information with reasonable fidelity for given values of the correlation length of the random parameter.     

High sensitivity CW-Cavity Ring Down Spectroscopy of five CO2 isotopologues of carbon dioxide in the 1.26-1.44 μm region (I): Line positions

The absorption spectrum of highly enriched ¹³C carbon dioxide has been investigated by CW-Cavity Ring Down Spectroscopy with a setup based on fibered distributed feedback (DFB) laser diodes. By using a series of 30 DFB lasers, the CO₂ spectrum was recorded in the 7029-7917 cm⁻¹ region with a typical sensitivity of 3×10⁻¹⁰ cm⁻¹. The uncertainty on the determined line positions is on the order of 8×10⁻⁴ cm⁻¹. More than 3800 transitions with intensities as low as 1×10⁻²⁹ cm/molecule were detected and assigned to the ¹³C¹⁶O₂, ¹⁶O¹³C¹⁷O, ¹⁶O¹³C¹⁸O, ¹⁷O¹³C¹⁸O and ¹³C¹⁸O₂ isotopologues. For comparison, only 104 line positions of ¹³C¹⁶O₂ were previously reported in the literature in the considered region. The band-by-band analysis has led to the determination of the rovibrational parameters of a total of 83 bands including 56 bands of the ¹³C¹⁶O₂ species. The measured line positions of ¹³C¹⁶O₂ and ¹⁶O¹³C¹⁸O were found in good agreement with the predictions of the respective effective Hamiltonian (EH) models but the agreement degrades for the minor isotopologues. Several cases of resonance interactions were found and discussed. In the 20033-10002 band of ¹³C¹⁶O₂, an anharmonic resonance interaction leads to deviations on the order of 0.05 cm⁻¹ compared to the EH predictions. The existence of interpolyad interactions affecting the non-symmetric isotopologues of carbon dioxide is confirmed by the observation of two occurrences in ¹⁶O¹³C¹⁷O and ¹⁶O¹³C¹⁸O. The obtained results improve significantly the knowledge of the spectroscopy of the ¹³C isotopologues of carbon dioxide. They will be valuable to refine the sets of effective Hamiltonian parameters used to generate the CDSD database.     

Kerr效应对双模二项式腔场谱的影响

研究了Kerr效应对单个二能级原子与二项式光场相互作用系统腔场谱的影响.研究发现,腔场谱结构对Kerr效应非常敏感,Kerr效应的轻微改变可使腔场谱结构明显变化,谱线劈裂、右移、间距增大、失去原有的对称性.在Kerr效应一定的情况下,一模腔场谱对另一模腔场的强弱也很敏感,一模腔场谱的增强可使另一模腔场谱线劈裂、右移、间距渐大,形成中心峰强,边峰弱,不对称的梳状结构.     

A FINITE ELEMENT METHOD WITH RECTANGULAR PERFECTLY MATCHED LAYERS FOR THE SCATTERING FROM CAVITIES

We develop a finite element method with rectangular perfectly matched layers （PMLs） for the wave scattering from two-dimensional cavities. The unbounded computational domain is truncated to a bounded one by using of a rectangular perfectly matched layer at the open aperture. The PML parameters such as the thickness of the layer and the fictitious medium property are determined through sharp a posteriori error estimates. Numerical experiments are carried out to illustrate the competitive behavior of the proposed method.     

Absorption and scattering characterization of airborne microparticulates by a cavity ringdown technique

Nonresonant cavity ringdown laser absorption spectroscopy (CRLAS) was applied for detection and characterization of airborne particulates. Sensitive detection of a variety of aerosols under ambient conditions was achieved. The method provides, for the first time, time-resolved absolute aerosol concentration, with spatial resolution (along a line). The first report on absorption spectroscopy of monodispersed aerosols (in the size range 100–200 nm) is provided, and comparisons are made with the bulk data. The results indicate the possibility of applying CRLAS for selective analysis of aerosols. A new method for estimating the aerosol refraction index is also obtained from the ringdown data.     

Cavity microelectrode for studying manganese dioxide powder as pH sensor

The potential-pH response of an electrolytic manganese dioxide is investigated by means of a cavity microelectrode (CME). The potential-pH curves show a complex evolution that could be explained by the disporportionation of MnOOH species, leading to the formation of Mn²⁺ ions on the MnO₂ surface. Such a behaviour is not suited for pH sensor application. However when the tip of the electrode is coated by a Nafion membrane, the potential-pH evolution shows a unique slope close to −60 mV pH⁻¹. In addition, the sensor exhibits short time responses to pH variations, a good selectivity, and it can be easily renewed compared to classical sensors.