Direct fit of experimental ro-vibrational intensities to the dipole moment function: Application to HCl

A dipole moment function (DMF) for hydrogen chloride (HCl) has been obtained using a direct fit approach that fits the best available and appropriately weighted experimental data for individual ro-vibrational transitions. Combining wavefunctions derived from the Rydberg-Klein-Rees (RKR) numerical method and a semi-empirical DMF, line intensities were calculated numerically for bands with Δv=0, 1, 2, 3, 4, 5, 6, 7 up to v′=7. The results have demonstrated the effectiveness of inclusion of rotational dipole moment matrix elements and appropriate weighting of the experimental data in the DMF fitting. The new method is shown to be superior to the common method of fitting only the rotationless dipole moment elements, while at the same time being simple to implement.     

Intensities of multiple-quantum coherences in a dilute spin system

The temporal evolution of the intensities of multiple-quantum coherences in a magnetically dilute system of dipole-dipole coupled spins is calculated. It is shown that not only the temporal scale but also the form of the time dependence itself are different from those in concentrated systems. Fiz. Tverd. Tela (St. Petersburg) 39, 510–512 (March 1997)     

Polarized infrared reflectivity study of an oriented ceramic of Bi 2 Sr 2 Ca 2 Cu 3 O 10 + δ (Bi-2223)

The reflectivity spectra of an oriented ceramic of Bi-2223 has been investigated by polarized infrared reflectivity spectroscopy in the energy range 0.005-2.2 eV. It is shown that the data for the polarization parallel to the c axis cannot be fitted with a one-component Drude or extended-Drude model. The conductivity spectrum is then obtained from the best fit of a “double-damping Drude” model to reflectivity spectra, itself derived from the factorized form of the dielectric function, and by a Kramers-Kronig inversion as well. The data and their analysis give a new insight of the 2D character of the system. Received 26 April 2001 and Received in final form 28 August 2001     

Inversion-rotation interaction in NH2D: Intensity perturbations in the ν2 band

The parameters of NH₂D in the ground and ν₂ states have been refined by a simultaneous analysis of the microwave, FTIR, and diode laser data. The intensities of 46 NH₂D lines have been measured, and from a least-squares fit of the intensity data the a ← s, s ← a, s ← s, and a ← a transition moments have been derived. The intensities of the lines in the ν₂ band of NH₂D have been calculated taking into account the inversion-rotation interaction. The accuracies of the wavenumbers and intensities calculated with the new parameters are estimated to be better than ±0.0002 cm⁻¹ and ±5%, respectively. The matrix elements for interaction of vibrations through x, y, and z axis couplings are appended.     

Simple Least-Squares Estimation of Intensities of Overlapping Signals in 2D NMR Spectra

It is described how a least-squares estimate of a two-dimensional NMR signal intensity can be calculated from two one-dimensional intensities, as estimated from a row and a column, respectively. The result is independent of artifacts associated with the Fourier transform, and it is unaffected by phase distortions and poor base plane definition in the spectrum. Cases of overlapping signals are discussed, and it is shown that because of the involved least-squares procedure, optimum results can be produced even when the overlap is substantial. Results of test calculations on simulated examples are presented, and it is shown that deviations of the calculated two-dimensional intensities from the correct values are small and in agreement with the standard deviations, also provided by the method. Finally, two-dimensional intensities calculated from experimental data are presented.     

O2A-band line parameters to support atmospheric remote sensing

Numerous satellite and ground-based remote sensing measurements rely on the ability to calculate O₂A-band [b¹Σ_g⁺←X³Σ_g⁻(0,0)] spectra from line parameters, with combined relative uncertainties below 0.5% required for the most demanding applications. In this work, we combine new ¹⁶O₂A-band R-branch measurements with our previous P-branch observations, both of which are based upon frequency-stabilized cavity ring-down spectroscopy. The combined set of data spans angular momentum quantum number, J′ up to 46. For these measurements, we quantify a J-dependent quadratic deviation from a standard model of the rotational distribution of the line intensities. We provide calculated transition wave numbers, and intensities for J′ up to 60. The calculated line intensities are derived from a weighted fit of the generalized model to an ensemble of data and agree with our measured values to within 0.1% on average, with a relative standard deviation of ≈0.3%. We identify an error in the calculated frequency dependence of the O₂A-band line intensities in existing spectroscopic databases. Other reported lineshape parameters include a revised set of ground-state energies, self- and air-pressure-broadening coefficients and self- and air-Dicke-narrowing coefficients. We also report a band-integrated intensity at 296 K of 2.231(7)×10⁻²² cm molec⁻¹ and Einstein-A coefficient of 0.0869(3) s⁻¹.     

Solid solutions of paradichlorobenzene in paradibromobenzene with vacancies present in their structure

The results of polarization studies of the low-frequency optical Raman spectra of solid solutions of paradibromobenzene with p-dichlorobenzene (10% paradichlorobenzene) are reported. The spectra of lattice vibrations of the mixed crystals are calculated, and it is shown that vacancies can be present in their structure, in agreement with the experimental spectra. The existence of vacancies is manifested by the appearance of secondary lines in the low-frequency spectrum, in the vicinity of 70 cm⁻¹. The intensities of the lines are related to the number of vacancies. The diffusion activation energies in mixed crystals of paradibromobenzene with paradichlorobenzene with vacancies present in their structure are calculated at different temperatures on the basis of the method of atom-atom potentials. It is shown that the activation energy in these mixed crystals is not as dependent on the temperature variation and the crystallographic direction as in crystals of the constituent components. Fiz. Tverd. Tela (St. Petersburg) 39, 1564–1566 (September 1997)     

Cosmic microwave background spectrum and G-varying cosmology

It is shown that G-varying cosmologies provide a better fit to the observed data on cosmic microwave background, than the standard Friedmann models.     

Calculations of molecular ir spectra in the overtone and combination frequency regions

Frequencies and intensities of fundamental, overtone, and combination absorption bands have been calculated in an anharmonic approximation for substituted benzene and ethene, aldehydes, ketones, and alcohols in the range 400–4000 cm^–1. The calculated values agree well with the experimental data. It is shown that such a calculation allows one to study and predict dependences of the frequencies and intensities of the overtone and combination bands on the substance structure.     

Calculation of the phase diagram of the GaInSb system in the (Ga +In)-rich region

The phase diagram of the GaInSb system in the (Ga + In)-rich region was calculated using the model of regular associated solutions (RAS). The calculated liquidus temperature and solidus composition surfaces were examined by a goodness of fit test derived for an (n + 1)-dimensional surface for which all the variables are subject to experimental errors. The results obtained using the RAS model were found to be in good agreement with the experimental data. It was also shown that the calculated phase diagram is compatible with the enthalpies of mixing measured for the GaIn, GaSb and InSb binary systems. Expressions were derived for the partial derivatives of the concentration of the various species in the liquid with respect to the temperature. Using these expressions it can be shown that, upon cooling, a liquid containing more (Ga + In) than Sb becomes super-saturated with regard to the atomic (uncombined) species and under-saturated with regard to the molecular species. Hence, the mechanism of crystallization proceeds via the addition of atomic layers to the surface of the crystal.     

Implications of neutron spectrum and flux differences on fission-fusion correlations at high neutron fluence

Abstract

The application to fusion environments of materials data derived from fission reactors involves considerations related not only to neutron spectra but also the often dominant effect of displacement rate. It is shown in this paper that fission-fusion correlation experiments directed toward helium effects and PKA recoil spectra are frequently difficult to interpret due to the strong influences of displacement rate, low energy recoils from thermal neutron absorption and in some cases a large influence of solid transmutants. It is also shown that materials data published in earlier decades must be reevaluated in light of recent advances in defining irradiation parameters.     

Effect of heavy atom disorder on the intensities of powder XRD lines of YBa2Cu3O7-y

Abstract

It is shown that heavy atom disorder resulting from Y ? Ba, Ba ? Cu and Y ? Cu interchanges due to local stoichiometric constraints can cause significant changes in the intensities of X-ray powder diffraction lines of YBa₂Cu₃O_7-y . A comparison of the theoretically predicted intensities with published patterns for specimens prepared by the conventional dry route reveals that Ba ? Cu interchanges involving copper atoms in the CuO₂ planes can occur quite frequently and may be mistaken for (00l) texture.     

On the enhancement of M1-transitions from neutron resonances in the Ba and Ce isotopes

The M1-strength functions for transitions from the ground states of ^136,138Ba and ¹⁴⁰Ce to the states lying near the neutron binding energy B_n are calculated within the quasiparticle-phonon nuclear model. The calculated M1-strength functions describe well the relevant experimental data. It is shown that a notable enhancement of the M1-transitions is caused by the proximity of the maximum of the M1-resonance to B_n. As a result the intensities of the E1 and M1-transitions appear to be close to each other.     

The static Debye-Waller factor of defect-induced lattice displacements

The attenuation of Bragg scattering intensities due to static displacements is discussed for interstitially dissolved point-defects. It is shown that in the single defect approximation the static Debye-Waller factor (DWF) exp (–2L) decreases linearly with the defect concentrationc and quadratically with the scattering-vectorK (for smallK andc). From a model calculation of the displacements around H in Nb the static DWF is shown to be primarily due to the displacements closest to the impurity. Therefore the measurement of the static DWF can be used as a method to determine these displacements. From X-ray measurements of the integrated Bragg intensities of NbH _x single crystals we obtained the displacements of the four nearest neighbours around a tetrahedral interstitial site to beu ₁=0.1Å. This is in good agreement with the results of our model calculation.     

Single nucleon distribution based on shell-model and matrix ensemble theory

An expression for the density of single nucleons in a heavy spherical nucleus is derived using the shell-model and matrix ensembles. It is shown that the theoretical expression gives an excellent fit to the density of nucleons for the nucleus¹⁹⁷Au obtained usinge-scattering data.     

<Emphasis Type="Italic">Ab initio</Emphasis> calculation of band absolute intensities in IR spectra

Ab initio calculations in a harmonic approximation of absorption band absolute intensities in infrared spectra were carried out for 3 hydrocarbons and 14 halogenated hydrocarbons. The calculated data were compared with experimental values of the absolute absorption intensities. It is shown that a Hartree–Fock calculation method overestimates significantly (by an average of 66%) the integrated absolute intensities of the fundamental bands in the region 575–4000 cm^–1. The deviation is reduced to 32% in the case of the MP2 method of accounting for electron correlations. Most of the overestimation occurs for bands corresponding to vibrations involving halogen atoms.     

Description of low-lying vibrationalK π≠0+ states of deformed nuclei in the quasiparticle-phonon nuclear model

The QPNM equations are derived taking account of p-h and p-p interactions. The calculated quadrupole, octupole and hexadecapole vibrational states in¹⁶⁸Er,¹⁷²Yb and¹⁷⁸Hf are found to be in reasonable agreement with experimental data. It is shown that distribution of theEλ strength in some deformed nuclei differs from the standard one. There are cases when for a givenK ^π theEλ strength is concentrated not on the first but on higher-lying states. The assertion made earlier about the absence of collective two-phonon states in deformed nuclei is confirmed.     

Fine-structure spectroscopy of 2-methylnaphthalene cooled in a supersonic jet

The fluorescence and fluorescence excitation spectra of 2-methylnaphthalene molecules cooled in a supersonic jet are measured. The frequencies of vibrations in the S ₀ and S ₁ states, as well as the relative intensities of electronic-vibrational transitions in the fluorescence and fluorescence excitation spectra, are calculated with the semiempirical MO/M8ST method. The intensities are calculated in the Franck-Condon approximation taking into account the mixing of all the 38 totally symmetric normal vibrations. Based on the calculations, most observed spectral lines are assigned. It is shown that the calculation accuracy of the method is high enough for it to be used to interpret the spectra of molecules of aromatic compounds such as substituted naphthalenes. It is found that the main contribution to the fluorescence spectrum is made by four optically active vibrations.     

Cusp satellite bands in the spectrum of molecule

We report measurements and a theoretical explanation of the cusp-shaped satellite bands in the blue wing of the cesium D₂ resonance line which have been observed for the first time. The bands are identified as transitions where the upper state dissociates into the 6 ²P _3/2 + 6 ² S _1/2 atomic asymptote. The experiment has been performed using a standard absorption setup, computer controlled data acquisition and computer data processing. We have shown that the peculiar shape of the difference-potential curve is solely responsible for the spectrum containing the cusp-shaped satellite bands. The appearance of these satellite bands has been discussed and explained relating the theory of satellite bands to the catastrophe theory. The shape of the line wing and of the satellite bands have been calculated using the Fourier transform technique. To ensure a more stringent comparison between the experimental and the theoretical spectrum, we have analyzed and compared the derivatives of the measured and the calculated satellite band shape. On the contrary to the customary direct comparison between the measured and the calculated absorption coefficient, the derivative clearly shows all differences and resemblances between satellite band profiles. The degree of coincidence of the experimentally observed and the theoretically calculated satellite band shape can be used as an ultimate check on the assessment of the quality of potential-energy curves involved in the formation of satellite bands. Received: 1 October 1997 / Revised: 14 January 1998 / Accepted: 24 February 1998