Scaled AMO calculations on the hydrogen molecule II. The 1s σ 2p σ 1∑ state

A scaled version of the AMO method is applied to the 1sσ2pσ ¹∑ state of the hydrogen molecule. A method to extend the domain of the mixing parameter λ to the whole complex plane is described and applied in the present calculation. All the parameters introduced have been varied completely. A considerable improvement in the computed energy values is found for large internuclear separations R. The comparison between our potential energy curve and the accurate curve calcualted by Kolos and Wolniewicz is studied and, for example, for R = 12 a.u. the energy difference is only 18% of that for R = 2.43 a.u. The equilibrium separation is found to be 2.140 a.u. in poor agreement with 2.429 a.u. obtained by the previously mentioned authors. In the separated atom limit, the state under consideration does not dissociate into H⁺ + H^?, although the ionic character of the wave function is dominating in the region 3 ≦ R ≦ 8 a.u. The connections with earlier calculations and methods, especially the scaled version of the MO –LCAO approximation, are also pointed out and discussed.     

Complexometric titration of Aluminium

A procedure is given for the complexometric titration of aluminium. A known volume of a standard solution of EDTA is added to the sample solution, and the excess is back-titrated with a zinc sulphate solution, dithizone being used as indicator. The titration is performed at pH = 4.0 — 4.5 and 40 — 50% alcohol is added as solvent for the indicator.The theoretical basis of the method is developed, and the theoretical titration error with various amounts of aluminium and zinc is calculated.The results of some titrations are given.     

On top-down splaying

The splay tree is a self-adjusting binary search tree which has a good amortized performance. This paper studies some properties of top-down splay trees. Different ways to charge for the primitive operations of top-down splaying are discussed. We also give some empirical results concerning the behaviour of different top-down restructuring algorithms.This work was supported by the Academy of Finland.     

Coherence of radiation as studied by multiple coincidences of photons and particles

Coincidences of photons and particles are measured by counting the number of events occurring simultaneously in two or more detectors. Coherent and incoherent radiation may have different behavior when the number of coincidence counts is studied with different arrangements of the coincidence detectors: the coincidence rate for the coherent radiation field, such as that obtained from a single-mode laser, is independent on the transverse separation between the detectors as long as the intensity of the radiation stays constant. On the other hand, with incoherent thermal radiation, using suitable monochromatization, the coincidence rate can show a significant bunching effect at detector separations smaller than the transverse coherence length. As a third alternative, photon antibunching may be observed if the radiation field is prepared in a number state, such as that available from resonance fluorescence of atoms, ions or molecules. If the time resolution of the detectors is not sufficient to resolve separate counts, corresponding effects can be observed in experiments, where the analog outputs of the detectors are multiplied to produce an intensity correlation signal. Intensity correlation and coincidence studies of photons and particles are reviewed in this report starting from the early experiments in the 1950’s and including recent work on X-ray coincidences and three-pion correlations. New results are presented for three- and four-photon coincidences at the X-ray wavelengths.     

Optical aperture area determination for accurate illuminance and luminous efficacy measurements of LED lamps

The measurement uncertainty of illuminance and, consequently, luminous flux and luminous efficacy of LED lamps can be reduced with a recently introduced method based on the predictable quantum efficient detector (PQED). One of the most critical factors affecting the measurement uncertainty with the PQED method is the determination of the aperture area. This paper describes an upgrade to an optical method for direct determination of aperture area where superposition of equally spaced Gaussian laser beams is used to form a uniform irradiance distribution. In practice, this is accomplished by scanning the aperture in front of an intensity-stabilized laser beam. In the upgraded method, the aperture is attached to the PQED and the whole package is transversely scanned relative to the laser beam. This has the benefit of having identical geometry in the laser scanning of the aperture area and in the actual photometric measurement. Further, the aperture and detector assembly does not have to be dismantled for the aperture calibration. However, due to small acceptance angle of the PQED, differences between the diffraction effects of an overfilling plane wave and of a combination of Gaussian laser beams at the circular aperture need to be taken into account. A numerical calculation method for studying these effects is discussed in this paper. The calculation utilizes the Rayleigh–Sommerfeld diffraction integral, which is applied to the geometry of the PQED and the aperture. Calculation results for various aperture diameters and two different aperture-to-detector distances are presented.     

Changes in Objective Acoustic Measurements and Subjective Voice Complaints in Call Center Customer-Service Advisors During One Working Day

SUMMARY: The aim of this study was to investigate how different acoustic parameters, extracted both from speech pressure waveforms and glottal flows, can be used in measuring vocal loading in modern working environments and how these parameters reflect the possible changes in the vocal function during a working day. In addition, correlations between objective acoustic parameters and subjective voice symptoms were addressed. The subjects were 24 female and 8 male customer-service advisors, who mainly use telephone during their working hours. Speech samples were recorded from continuous speech four times during a working day and voice symptom questionnaires were completed simultaneously. Among the various objective parameters, only F0 resulted in a statistically significant increase for both genders. No correlations between the changes in objective and subjective parameters appeared. However, the results encourage researchers within the field of occupational voice use to apply versatile measurement techniques in studying occupational voice loading.     

Acoustic Measures and Self-reports of Vocal Fatigue by Female Teachers

This study investigated the relation of symptoms of vocal fatigue to acoustic variables reflecting type of voice production and the effects of vocal loading. Seventy-nine female primary school teachers volunteered as subjects. Before and after a working day, (1) a 1-minute text reading sample was recorded at habitual loudness and loudly (as in large classroom), (2) a prolonged phonation on [a:] was recorded at habitual speaking pitch and loudness, and (3) a questionnaire about voice quality, ease, or difficulty of phonation and tiredness of throat was completed. The samples were analyzed for average fundamental frequency (F0), sound pressure level (SPL), and phonation type reflecting alpha ratio (SPL [1-5 kHz]-SPL [50 Hz-1 kHz]). The vowel samples were additionally analyzed for perturbation (jitter and shimmer). After a working day, F0, SPL, and alpha ratio were higher, jitter and shimmer values were lower, and more tiredness of throat was reported. The average levels of the acoustic parameters did not correlate with the symptoms. Increase in jitter and mean F0 in loud reading correlated with tiredness of throat. The results seem to suggest that, at least among experienced vocal professionals, voice production type had little relevance from the point of view of vocal fatigue reported. Differences in the acoustic parameters after a vocally loading working day mainly seem to reflect increased muscle activity as a consequence of vocal loading.     

Stark effect and generalized Bloch-Siegert shift in a strongly driven two-level system

A superconducting qubit was driven in an ultrastrong fashion by an oscillatory microwave field, which was created by coupling via the nonlinear Josephson energy. The observed Stark shifts of the "atomic" levels are so pronounced that corrections even beyond the lowest-order Bloch-Siegert shift are needed to properly explain the measurements. The quasienergies of the dressed two-level system were probed by resonant absorption via a cavity, and the results are in agreement with a calculation based on the Floquet approach.     

Isotopic pattern and accurate mass determination in urine drug screening by liquid chromatography/time-of-flight mass spectrometry

An efficient method was developed for toxicological drug screening in urine by liquid chromatography coupled with electrospray ionization time-of-flight mass spectrometry. The method relies on a large target database of exact monoisotopic masses representing the elemental formulae of reference drugs and their metabolites. Mass spectral identification is based on matching measured accurate mass and isotopic pattern (SigmaFit) of a sample component with those in the database. Data post-processing software was developed for automated reporting of findings in an easily interpretable form. The mean and median of SigmaFit for true-positive findings were 0.0066 and 0.0051, respectively. The mean and median of mass error absolute values for true-positive findings were 2.51 and 2.17 ppm, respectively, corresponding to 0.65 and 0.60 mTh. For routine screening practice, a SigmaFit tolerance of 0.03 and a mass tolerance of 10 ppm were chosen. Ion abundance differences from urine extracts did not affect the accuracy of the automatically acquired SigmaFit or mass values. The results show that isotopic pattern matching by SigmaFit is a powerful means of identification in addition to accurate mass measurement.     

Rapid identification and quantitation of compounds with forensic interest using fast liquid chromatography-ion trap mass spectrometry and library searching

A fast liquid chromatography-electrospray tandem mass spectrometric (LC-ESI-MS-MS) method by using a monolithic column, gradient elution and ion trap mass spectrometer was developed for 14 forensically interesting and chemically different compounds. All compounds were eluted within 2.5 min and the total analysis time was 5 min including stabilisation time required for the next injection. All the compounds, basics, neutrals and acids were efficiently ionised by positive ion ESI. A laboratory library including MS-MS spectra and retention times was developed and tested. Results with 476 standard samples and 50 authentic samples showed that the compounds studied can be unambiguously identified with the library. A quantitative method was developed for the compounds using external calibration. The evaluation process showed good linearity of the method and reasonable repeatability. Limits of detection ranged from 10.0 to 50.0 ng/ml.