Theoretical calculations of pressure broadening coefficients for H2O perturbed by hydrogen or helium gas

Halfwidths were calculated for H2O with H2 as a broadening gas and were estimated for He as the broadening species. The calculations used the model of Robert and Bonamy with parabolic trajectories and all relevant terms in the interaction potential. The calculations investigated the dependence of the halfwidth on the order of the atom-atom expansion, the rotational states, and the temperature in the range 200 to 400K. Finally, calculations were performed for many transitions of interest in the 5 micrometer window region of the spectrum. The resulting data will be supplied to Dr. R. Freedman for extracting accurate water mixing ratios from the analysis of the thermal channels for the Net Flux experiment on the Galileo probe

An intercomparison of measured pressure-broadening, pressure shifting parameters of carbon dioxide and their temperature dependence

International audienceAn intercomparison of measured pressure-broadening and pressure-shifting coefficients for carbon dioxide absorption lines was done. The work focuses on collision systems where a significant number of data can be found (CO2-N2, CO2-O2, CO2-air, and CO2-CO2) and yield information important to applications related to Earth's atmosphere. The literature was searched for measured line shape parameter data for the collision systems mentioned above. Databases were created for each perturbing gas with the ro-vibrational transition as the key. Using these databases intercomparisons of the measurements of half-widths, their temperature dependence, and line shifts were made. The data allow the investigations of trends in the data with respect to the vibrational and the rotational quantum numbers, various line shape models, and isotopologue effects

Experimental AR Fault Detection Methods for a Hydraulic Robot

This paper focuses on practical use and theoretical elaboration of the analytical redundancy technique which is used to efficiently detect faults that have been determined to be mission-hazardous by previous FMECA and fault tree analyses of the Rosie system. We believe we have contributed significant improvements to the potential overall reliability of the system. Additionally, we have expanded the applicability of the AR method to nonlinear systems in the course of our work, making this valuable fault detection method more broadly applicable.National Science FoundationSandia National Laborator

Statistical distributions of consonant variants in infant-directed speech: evidence that /t/ may be exceptional

Statistical distributions of phonetic variants in spoken language influence speech perception for both language learners and mature users. We theorized that patterns of phonetic variant processing of consonants demonstrated by adults might stem in part from patterns of early exposure to statistics of phonetic variants in infant-directed (ID) speech. In particular, we hypothesized that ID speech might involve greater proportions of canonical /t/ pronunciations compared to adult-directed (AD) speech in at least some phonological contexts. This possibility was tested using a corpus of spontaneous speech of mothers speaking to other adults, or to their typically-developing infant. Tokens of word-final alveolar stops – including /t/, /d/, and the nasal stop /n/ – were examined in assimilable contexts (i.e., those followed by a word-initial labial and/or velar); these were classified as canonical, assimilated, deleted, or glottalized. Results confirmed that there were significantly more canonical pronunciations in assimilable contexts in ID compared with AD speech, an effect which was driven by the phoneme /t/. These findings suggest that at least in phonological contexts involving possible assimilation, children are exposed to more canonical /t/ variant pronunciations than adults are. This raises the possibility that perceptual processing of canonical /t/ may be partly attributable to exposure to canonical /t/ variants in ID speech. Results support the need for further research into how statistics of variant pronunciations in early language input may shape speech processing across the lifespan

Structure-Function Model for Kissing Loop Interactions That Initiate Dimerization of Ty1 RNA

The genomic RNA of the retrotransposon Ty1 is packaged as a dimer into virus-like particles. The 5′ terminus of Ty1 RNA harbors cis-acting sequences required for translation initiation, packaging and initiation of reverse transcription (TIPIRT). To identify RNA motifs involved in dimerization and packaging, a structural model of the TIPIRT domain in vitro was developed from single-nucleotide resolution RNA structural data. In general agreement with previous models, the first 326 nucleotides of Ty1 RNA form a pseudoknot with a 7-bp stem (S1), a 1-nucleotide interhelical loop and an 8-bp stem (S2) that delineate two long, structured loops. Nucleotide substitutions that disrupt either pseudoknot stem greatly reduced helper-Ty1-mediated retrotransposition of a mini-Ty1, but only mutations in S2 destabilized mini-Ty1 RNA in cis and helper-Ty1 RNA in trans. Nested in different loops of the pseudoknot are two hairpins with complementary 7-nucleotide motifs at their apices. Nucleotide substitutions in either motif also reduced retrotransposition and destabilized mini- and helper-Ty1 RNA. Compensatory mutations that restore base-pairing in the S2 stem or between the hairpins rescued retrotransposition and RNA stability in cis and trans. These data inform a model whereby a Ty1 RNA kissing complex with two intermolecular kissing-loop interactions initiates dimerization and packaging

Impact of level of personality pathology on affective, behavioral, and thought problems in pregnant women during the Coronavirus Disease 2019 pandemic

Among at-risk groups for psychological distress in the context of the Coronavirus Disease 2019 (COVID-19) pandemic, pregnant women might be especially vulnerable. Identifying subgroups of pregnant women at high risk of poor adaptation might optimize clinical screening and intervention, which could, in turn, contribute to mitigating the potentially devastating effects of prenatal stress on mothers and fetus. Level of personality functioning may be a good indicator of who may be more vulnerable to distress in challenging periods like the COVID-19 pandemic, as adults with high levels of personality dysfunction may experience significant difficulties in mentalizing threatening situations. The aims of the present study are (a) to determine the impact of level of personality pathology on affective, behavioral, and thought problems in pregnant women during the COVID-19 pandemic; and (b) to test a model where mentalization of trauma mediates the impact of personality pathology on symptomatology. Data from 1,207 French-Canadian pregnant women recruited through social media during the COVID-19 pandemic were analyzed. Latent profile analysis, using the Criterion A elements of the alternative model for personality disorders (Identity, Self-Direction, Empathy, Intimacy) as latent indicators, yielded four profiles: Healthy, Mild Self-Impairment, Intimacy Impairment, and Personality Disorder. Profiles showed significant associations with diverse indicators of symptomatology. Mediation models showed both direct and indirect (through mentalization of trauma) significant associations between level of personality functioning and affective/behavioral/thought problems. Results have clinical implications on prophylactic measures for at-risk pregnant women, especially in challenging contexts such as the COVID-19 pandemic

Theoretical calculations of N 2-broadened half-widths of n 5

N 2 -broadening Temperature dependence of half-width Vibrational and rotational state dependence a b s t r a c t A number of satellite instruments are measuring nitric acid, HNO 3 , in the Earth's atmosphere. In order to do retrievals of temperature and concentration profiles, the spectral parameters for many thousands of HNO 3 transitions must be known. Currently the HITRAN database uses a constant estimated value for the air-broadened half-width of HNO 3 . To help improve the line shape parameters, complex Robert-Bonamy calculations were made to determine N 2 -broadened half-widths for some 5000 transitions of HNO 3 in the n 5 band. The intermolecular potential is a sum of electrostatic terms (dipole-quadrupole and quadrupole-quadrupole) and the atom-atom potential expanded to eighth order. The trajectory parameters were adjusted to yield better agreement with measurement. Velocity integrated calculations were made at seven temperatures in order to determine the temperature dependence of the half-widths. The half-width data are compared with available rotation band measurements. The average percent difference between the measured and calculated half-widths is À2.38 for N 2 -broadening and À0.65 for air-broadening. The temperature, vibrational, and rotational state dependence of the half-width are investigated

IUPAC Critical Evaluation of the Rotational-Vibrational Spectra of Water Vapor, Part III: Energy Levels and Transition Wavenumbers for H216O

This is the third of a series of articles reporting critically evaluated rotational-vibrational line positions, transition intensities, and energy levels, with associated critically reviewed labels and uncertainties, for all the main isotopologues of water. This paper presents experimental line positions, experimental-quality energy levels, and validated labels for rotational-vibrational transitions of the most abundant isotopologue of water, H216O. The latest version of the MARVEL (Measured Active Rotational-Vibrational Energy Levels) line-inversion procedure is used to determine the rovibrational energy levels of the electronic ground state of H216O from experimentally measured lines, together with their self-consistent uncertainties, for the spectral region up to the first dissociation limit. The spectroscopic network of H216O contains two components, an ortho (o) and a para (p) one. For o-H216O and p-H216O, experimentally measured, assigned, and labeled transitions were analyzed from more than 100 sources. The measured lines come from one-photon spectra recorded at room temperature in absorption, from hot samples with temperatures up to 3000K recorded in emission, and from multiresonance excitation spectra which sample levels up to dissociation. The total number of transitions considered is 184667 of which 182156 are validated: 68027 between para states and 114129 ortho ones. These transitions give rise to 18486 validated energy levels, of which 10446 and 8040 belong to o-H216O and p-H216O, respectively. The energy levels, including their labeling with approximate normal-mode and rigid-rotor quantum numbers, have been checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators as well as against previous compilations of energy levels. The extensive list of MARVEL lines and levels obtained are deposited in the supplementary data of this paper, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved

Recommended isolated-line profile for representing high-resolution spectroscopic transitions (IUPAC Technical Report)

The report of an IUPAC Task Group, formed in 2011 on "Intensities and line shapes in high-resolution spectra of water isotopologues from experiment and theory" (Project No. 2011-022-2-100), on line profiles of isolated high-resolution rotational-vibrational transitions perturbed by neutral gas-phase molecules is presented. The well-documented inadequacies of the Voigt profile (VP), used almost universally by databases and radiative-transfer codes, to represent pressure effects and Doppler broadening in isolated vibrational-rotational and pure rotational transitions of the water molecule have resulted in the development of a variety of alternative line-profile models. These models capture more of the physics of the influence of pressure on line shapes but, in general, at the price of greater complexity. The Task Group recommends that the partially Correlated quadratic-Speed-Dependent Hard-Collision profile should be adopted as the appropriate model for high-resolution spectroscopy. For simplicity this should be called the Hartmann--Tran profile (HTP). The HTP is sophisticated enough to capture the various collisional contributions to the isolated line shape, can be computed in a straightforward and rapid manner, and reduces to simpler profiles, including the Voigt profile, under certain simplifying assumptions.Comment: Accepted for publication in Pure and Applied Chemistr