Semi-empirical calculation of air-broadened half-widths and air pressure-induced frequency shifts of water-vapor absorption lines

This paper describes a semi-empirical calculation of the air-broadened half-widths and the air pressure-induced frequency shifts for the H₂¹⁶O isotopologue. This semi-empirical calculation is based on fits of several recent high-quality measurements and theoretical calculations to the first-order terms in the expansion of the complex Robert-Bonamy (CRB) equations, which yields a second- and first-order polynomial function of the differences in the upper- and lower-state vibrational quantum numbers for the half-width and line shift, respectively. The aim of this work was to obtain a complete set of air-broadened half-widths and air pressure-induced frequency shifts for transitions of H₂¹⁶O present in the HITRAN database from microwave to the visible in order to supplement the observed and calculated values. For around 700 sets of rotational quantum numbers (), semi-empirical coefficients describing the vibrational dependence of the air-broadened half-widths and the air pressure-induced frequency shifts have been obtained directly from the fit of experimental and/or theoretical data. The accuracy of the parameters deduced from this calculation is estimated to be between 5% and 10% for the air-broadened half-widths and between 0.001 and for the air pressure-induced frequency shifts. For sets of rotational quantum numbers for which either none or insufficient experimental/theoretical data were available to deduce a vibrational dependence, further approximations have been used to obtain a complete set of semi-empirical coefficients.     

4-benzyl pyridinium dihydrogenmonophosphate C6H5CH2C5H4NHH2PO4 : Single-crystal structure and its conductivity in polycrystalline form

The salt 4-benzyl pyridinium dihydrogenmonophosphate is monoclinic P2₁/c with the following unit cell dimensions: ; ; ; and β=97.328(11). Also, , D_x=1.403, , F(000)=560; ; and R=0.0495 and R_w=0.0964 for 3733 independent reflections. The structure consists of infinite parallel two-dimensional planes built of H₂PO₄⁻ anions and C₆H₅CH₂C₅H₄NH⁺ cations mutually connected by strong O-H ?O and N-H ?O hydrogen bonding. There are no contacts other than the normal Van der Waals interactions between the layers. The conductivity relaxation parameters associated with some H⁺ conduction have been determined from an analysis of the spectrum measured in a wide temperature range.     

Quantum mechanics of Klein-Gordon-type fields and quantum cosmology

With a view to address some of the basic problems of quantum cosmology, we formulate the quantum mechanics of the solutions of a Klein-Gordon-type field equation: (∂_t²+D)ψ(t)=0, where and D is a positive-definite operator acting in a Hilbert space . In particular, we determine all the positive-definite inner products on the space of the solutions of such an equation and establish their physical equivalence. This specifies the Hilbert space structure of uniquely. We use a simple realization of the latter to construct the observables of the theory explicitly. The field equation does not fix the choice of a Hamiltonian operator unless it is supplemented by an underlying classical system and a quantization scheme supported by a correspondence principle. In general, there are infinitely many choices for the Hamiltonian each leading to a different notion of time-evolution in . Among these is a particular choice that generates t-translations in and identifies t with time whenever D is t-independent. For a t-dependent D, we show that regardless of the choice of the inner product the t-translations do not correspond to unitary evolutions in , and t cannot be identified with time. We apply these ideas to develop a formulation of quantum cosmology based on the Wheeler-DeWitt equation for a Friedman-Robertson-Walker model coupled to a real scalar field with an arbitrary positive confining potential. In particular, we offer a complete solution of the Hilbert space problem, construct the observables, use a position-like observable to introduce the wave functions of the universe (which differ from the Wheeler-DeWitt fields), reformulate the corresponding quantum theory in terms of the latter, reduce the problem of the identification of time to the determination of a Hamiltonian operator acting in , show that the factor-ordering problem is irrelevant for the kinematics of the quantum theory, and propose a formulation of the dynamics. Our method is based on the central postulates of nonrelativistic quantum mechanics, especially the quest for a genuine probabilistic interpretation and a unitary Schrödinger time-evolution. It generalizes to arbitrary minisuperspace (spatially homogeneous) models and provides a way of unifying the two main approaches to the canonical quantum cosmology based on these models, namely quantization before and after imposing the Hamiltonian constraint.     

Time-resolved infrared diode laser spectroscopy of the ν1 (C-O stretch) band of the CoCO radical

Infrared spectrum of the cobalt carbonyl radical CoCO produced by the 193 nm excimer laser photolysis of cobalt tricarbonyl nitrosyl Co(CO)₃NO was observed by time-resolved diode laser spectroscopy. More than 600 lines were identified as belonging to the ν₁ (C-O stretch) fundamental band, consisting of the Ω=5/2 and 3/2 subbands, and the associated hot bands , , , and . The ²Δ_i electronic ground state of CoCO was experimentally confirmed. The ν₁ band origins are 1974.172582(93) cm⁻¹ and 1973.53178(14) cm⁻¹ for the Ω=5/2 and 3/2 subbands, respectively. The rotational constant in the ground state was determined as B₀=4427.146(50) MHz. The centrifugal distortion constant D₀=1.1243(68) kHz was obtained for the Ω=5/2 substate of the ground state. The equilibrium rotational constant B_e=4435.44(14) MHz was derived, together with the vibration-rotation interaction constants.     

Relaxor behavior of K0.5La0.5Bi2Ta2O9 ceramics

Potassium lanthanum bismuth tantalate (K_0.5La_0.5Bi₂Ta₂O₉), a new relaxor ferroelectric was synthesized via the solid-state reaction route. X-ray structural studies along with Rietveld refinement confirmed it to be an n=2 member of the Aurivillius family of oxides and the refined lattice parameters are , and . The appearance of 1/2{h00} and 1/2{hk0} type superlattice reflections in the electron diffraction patterns reflected the presence of ordered polar regions. A broad dielectric peak associated with frequency dependent dielectric maximum temperature was observed. The value of the diffuseness parameter γ=1.93, obtained from the fit of a modified Curie-Weiss law established the relaxor nature of the title compound. The dielectric relaxation obeyed the Vogel-Fulcher relation wherein and . The relaxor behavior was attributed to the local polar ordering on A-sites.