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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Inorganic chemistry 23 (1984), S. 184-189 
    ISSN: 1520-510X
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1520-510X
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1520-510X
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
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  • 4
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Analytical chemistry 54 (1982), S. 1899-1901 
    ISSN: 1520-6882
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
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  • 5
    ISSN: 1420-9136
    Keywords: Earthquake precursors ; clustering ; quiescence ; earthquake statistics ; seismicity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract This paper describes a new method, single-link cluster analysis (SLC), to evaluate percursory quiescence for shallow earthquakes in sixteen subduction zones, using data from the ISC catalog. To define quiescent regions, we divided the catalog into time intervals with a durationT, overlapping byT/2. We considered all earthquakes having magnitudes larger than some magnitudeM min, lying within a specified distance of a great circle which is approximately coincident with the trench near a subduction zone. Within each time interval we connected or ‘linked’ all earthquakes lying within some cutoff distanced of one another. We then projected all these links onto the great circle, and defined a region to be quiescent if it was not covered by the projection of any links. For this study,T was two years,M min wasm b =4.9, and we variedd from 100 to 400 km. We defined an earthquake as ‘following quiescence’ if it occurred within two years following, and within 75 km of a quiescent zone as defined above. The primary conclusion of this study was that earthquakes with surface wave magnitudes 7.2 and greater were about 5–15% more likely to follow quiescence than were the smaller background earthquakes withm b 〉-4.9. A chi-squared analysis shows that this result is significant at the 99% level. In contrast, earthquakes with surface wave magnitude of 6.7 to 7.1 were no more likely to follow quiescence than were background earthquakes. Of sixteen individual regions, Central America, Japan, and Peru-Chile were the only regions where large earthquakes were more likely to occur following quiescence than were background earthquakes. For a cutoff link length of 300 km, only in Central America was the difference between large earthquakes and background earthquakes significant at the 95% level of significance. For a cutoff link length of 250 km, the significance level exceeded 95% only in Japan. The SLC method is an objective, quantitative method for evaluating large data catalogs, or for monitoring quiescence in regions where quiescence is conjectured to precede large earthquakes.
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  • 6
    ISSN: 1432-1432
    Keywords: Key words: Bottleneck — Genetic diversity — Linkage disequilibrium — Null allele — Bowhead whale
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract. A size-selected Balaena mysticetus genomic library was screened for clones containing simple sequence repeat, or microsatellite, loci. A total of 11 novel loci was identified. These loci were combined with a set of 9 published loci, for a total of 20 markers, and were scored across a sample of 108 bowhead whales from the Bering–Chukchi–Beaufort Seas population of bowhead whales. Genetic variability was measured in terms of polymorphism information content values and unbiased heterozygosity. From the latter, estimates of long-term effective population size were obtained. In addition, gametic phase disequilibrium among loci was investigated. Moderate to high levels of polymorphism were found overall, and the long-term effective size estimates were large relative to total population size. Tests of heterozygosity excess (Cornuet and Luikart 1996) and allele frequency distribution (Luikart et al. 1998) indicated that the possibility of a recent genetic bottleneck in the Bering–Chukchi–Beaufort Seas population of bowhead whales is highly unlikely. However, the fact that five loci displayed a statistically significant heterozygote deficiency remains to be explained.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 116 (2002), S. 6132-6145 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High resolution infrared spectra of the two "low" frequency intermolecular modes—van der Waals stretch (ν4) and geared bend (ν5) of (HCl)2—have been characterized in HCl-stretch excited states using a slit jet spectrometer. In a high resolution high sensitivity search covering the range between 2880 and 3070 cm−1 four (HCl)2 combination bands associated with in-plane vibrations ν4 and ν5 have been observed. The vibrational assignment of these bands is based on comparison between observed intermolecular mode energies and predictions from recent six-dimensional (6D) quantum mechanical (QM) calculations [Y. Qiu, J. Z. H. Zhang, and Z. Bacic, J. Chem. Phys. 108, 4804 (1998)], though additional confirmation is provided by ancillary spectroscopic information such as rotational constants, predissociation linewidths, and 35Cl/37Cl isotopic band shifts. The experimentally observed intermolecular energies agree with theoretical predictions to (approximate)2–4 cm−1 out of 60–90 cm−1, suggesting that the 6D potential energy surface can describe combination band excitation in these lower frequency intermolecular coordinates fairly well. Three of the four observed combination bands arise from the upper tunneling level (B+), and all four bands are built exclusively on bound HCl stretch (ν2). To account for these striking intensity anomalies, a simple model for three-dimensional QM calculation of transition moments is introduced, which correctly reproduces the experimental trends. In this model, the propensity for ν2 based combination bands arising from upper tunneling levels can be successfully ascribed to the unusually "floppy" nature of the intermolecular vibrations, which results in a "harmonic oscillator" Δv=+1 propensity for excitations between tunneling levels along the geared bend coordinate. © 2002 American Institute of Physics.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 116 (2002), S. 6146-6158 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Transitions to overtone 2ν2 and 2ν3, and combination ν2+ν3 vibrations in jet-cooled H2D+ and D2H+ molecular ions have been measured for the first time by high-resolution IR spectroscopy. The source of these ions is a pulsed slit jet supersonic discharge, which allows for efficient generation, rotational cooling, and high frequency (100 KHz) concentration modulation for detection via sensitive lock-in detection methods. Isotopic substitution and high-resolution overtone spectroscopy in this fundamental molecular ion permit a systematic, first principles investigation of Born–Oppenheimer "breakdown" effects due to large amplitude vibrational motion as well as provide rigorous tests of approximate theoretical methods beyond the Born–Oppenheimer level. The observed overtone transitions are in remarkably good agreement (〈0.1 cm−1) with non-Born–Oppenheimer ab initio theoretical predictions, with small but systematic deviations for 2ν2, ν2+ν3, and 2ν3 excited states indicating directions for further improvement in such treatments. Spectroscopic assignment and analysis of the isotopomeric transitions reveals strong Coriolis mixing between near resonant 2ν3 and ν2+ν3 vibrations in D2H+. Population-independent line intensity ratios for transitions from common lower states indicate excellent overall agreement with theoretical predictions for D2H+, but with statistically significant discrepancies noted for H2D+. Finally, H2D+ versus D2H+ isotopomer populations are analyzed as a function of D2/H2 mixing ratio and can be well described by steady state kinetics in the slit discharge expansion. © 2002 American Institute of Physics.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 1823-1834 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A glow discharge, slit supersonic expansion in conjunction with direct infrared laser absorption methods has been utilized to record high resolution vibration–rotation spectra of the CH3–CH2 ethyl radical. The slit supersonic expansion results in efficient rotational cooling from discharge temperatures down to Trot(approximate)14 K, permitting unambiguous rotational assignment and spectral analysis for the first time. Furthermore, a discharge on/discharge off data collection scheme permits clean discrimination between spectral contributions from radical vs precursor absorption. Spectra for both symmetric and asymmetric CH2 stretch manifolds are observed. Least-squares fits of transition frequencies out of the K=0 ground state manifold to a near prolate top model Hamiltonian reproduce the data to within the 7 MHz experimental uncertainty and provides rotational constants for both ground and vibrationally excited symmetric/asymmetric CH2 stretch states. The band origins for the CH2 stretch vibrations [3037.018 96(12) cm−1 and 3128.693 69(13) cm−1] are in reasonable agreement with ab initio theory; though predictions for relative intensities of the two bands are off by nearly an order of magnitude and indicate that the transition moment vector is tilted 33° away from each C–H bond toward the C–C bond axis. Structural analysis based on the measured B and C rotational constants imply a C–C bond distance of 1.49 Å. This is consistent with partial ((approximate)15%) double bond character for the ethyl radical carbon frame and in excellent agreement with theoretical predictions. © 2000 American Institute of Physics.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 225-235 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rotationally resolved S1←S0 fluorescence excitation spectra of 2-chloronaphthalene (2ClN) are measured using a newly constructed ultraviolet (UV) laser/molecular beam spectrometer. More than 1000 well-resolved rotational lines are recorded at a resolution of ∼3 MHz for the two overlapping band origins of the 35Cl and 37Cl isotopomers (Δνorigin∼3 GHz) over a 3.5 cm−1 spectral region at a rotational temperature of 10 K. Both spectra are hybrid bands, having 18% a-/82% b-type character in accordance with 1La←1A1 excitations observed for other 2-substituted naphthalenes. Additionally, Cl nuclear quadrupole splittings are observed as broadened asymmetric line shapes with linewidths from 5 to 20 MHz. Least-squares fits of these line shapes coupled with high-precision Fourier-transform microwave measurements of the ground state have provided accurate S1 quadrupole coupling constants. Specified relative to the principal quadrupole tensor orientation of S0, the S0 and S1 values of eQqzz are −71.198(5) MHz and −67.8(30) MHz, and the asymmetry parameters, η=(eQqyy−eQqxx)/eQqzz, are 0.076 38(5) and 0.13(5), respectively. The experimental line shapes are fit to Voigt functions, yielding 4.9(3) MHz homogeneous (lifetime) and 3.0(2) MHz inhomogeneous (Doppler) contributions. All of the observed structure are well reproduced by more than 20 000 transitions predicted for the nuclear-quadrupole-split rotational spectra of the two hybrid-band origins. Furthermore, the homogeneous linewidths show no dependence on either the upper state energy or angular momentum quantum numbers. The absence of additional level structure at the resolution of 1 MHz or more, from heavy-atom-enhanced intersystem crossing mechanisms, is discussed within the framework of radiationless transition theory. The quadrupole tensor components are used in simple theoretical models to investigate the orbital character of the S1 state and its radiationless decay mechanisms. © 2001 American Institute of Physics.
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