9 research outputs found
Examination of Low-Lying Rovibrational States of D3h Oblate Top Molecules Using High Resolution FTIR and Coherent Anti-Stokes Raman Spectroscopies
No full textInteresting rovibrational characteristics of two D 3h oblate symmetric top molecules were studied. Hamiltonian models for the fine rovibrational level structure of [1.1.1]propellane (propellane) were obtained for many low-lying modes. Ground state parameters (GSP) that are not exclusively K2n dependent were obtained. Initially, the GSP were used in conjunction with density functional (DFT) values of the exclusively K2n dependent parameters C0, and De. Coriolis h1,1 (ΔK = ± 1, Δ l = ± 1) interactive fundamentals ν15 and ν 12 were analyzed; complementary use of transition energies and line intensities allowed an experimental value of the Coriolis parameter to be assessed. In another phase of the project, a global fit of the ν10 , ν11, and ν14 fundamental bands and the ν 11-ν18 and ν10-ν18 bands was performed. The h1,1 interaction between the close proximity rovibrational states of ν11 and ν14 results in energy shifts and large distortions of line intensities in the ν 11 band, and these characteristics were reproduced. Splitting of the otherwise degenerate A1 and A 2 states that are the highest in frequency for a given J manifold was observed for the h1,1 coupled ν 11 /ν14 triad composed of the |k| = 3 levels of ν14, the kl = + 4 levels of ν11, and kl = −2 levels of ν 11. Significant splitting of the kl = −2 levels in combination with h1,1 are important in the noted lifting of degeneracies. Another interaction, this one between ν14 and what is presumably the IR inactive ν16/ν 3 singly excited dyad, results in a significant bifurcation of the K levels of ν14 for a given observable J manifold. Another interaction, h5,−1, between ν 14 and ν11, made it possible to find C 0 and DK0, parameters not available from analysis of transitions from the ground vibrational state to singly excited fundamentals in the absence of higher order interactions. In studies of another D3h oblate top, BF3, effects of anharmonic interactions on the band origin of the symmetric stretching mode were examined using coherent anti-Stokes Raman spectra of 10BF 3 and 11BF3. Upon isotopic substitution, the magnitude and direction of the anharmonic shifts of each fundamental were observed to be consistent with DFT results
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Examination of low-lying rovibrational states of D₃[subscript h] oblate top molecules using high resolution FTIR and coherent anti-Stokes Raman spectroscopies
No full textInteresting rovibrational characteristics of two D_(3h) oblate symmetric top molecules were studied. Hamiltonian models for the fine rovibrational level structure of [1.1.1]propellane (propellane) were obtained for many low-lying modes. Ground state parameters (GSP) that are not exclusively K^(2n) dependent were obtained. Initially, the GSP were used in conjunction with density functional (DFT) values of the exclusively K^(2n) dependent parameters C_0, and D_e. Coriolis h_(1,1) (deltaK = +/-1, deltal = +/-1) interactive fundamentals nu_(15) and nu_(12) were analyzed; complementary use of transition energies and line intensities allowed an experimental value of the Coriolis parameter to be assessed. In another phase of the project, a global fit of the nu_(10), nu_(11), and nu_(14) fundamental bands and the nu_(11)-nu_(18) and nu_(10)-nu_(18) bands was performed. The h_(1,1) interaction between the close proximity rovibrational states of nu_(11) and nu_(14) results in energy shifts and large distortions of line intensities in the nu_(11) band, and these characteristics were reproduced. Splitting of the otherwise degenerate A_1 and A_2 states that are the highest in frequency for a given J manifold was observed for the h_(1,1) coupled nu_(11) /nu_(14) triad composed of the |k| = 3 levels of nu_(14) , the kl = + 4 levels of nu_(11), and kl = -2 levels of nu_(11). Significant splitting of the kl=-2 levels in combination with h_(1,1) are important in the noted lifting of degeneracies. Another interaction, this one between nu_(14) and what is presumably the IR inactive nu_(16)/nu_3 singly excited dyad, results in a significant bifurcation of the K levels of nu_(14) for a given observable J manifold. Another interaction, h_(5,-1), between nu(14) and nu_(11), made it possible to find C_0 and D_K 0, parameters not available from analysis of transitions from the ground vibrational state to singly excited fundamentals in the absence of higher order interactions. In studies of another D_(3h) oblate top, BF_3, effects of anharmonic interactions on the band origin of the symmetric stretching mode were examined using coherent anti-Stokes Raman spectra of ^(10)BF_3 and ^(11)BF_3. Upon isotopic substitution, the magnitude and direction of the anharmonic shifts of each fundamental were observed to be consistent with DFT results
COHERENT RAMAN SPECTRA OF THE MODE OF BF AND BF
No full textAuthor Institution: Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, OR 97331-4003; Pacific Northwest National Laboratory, P. O. Box 999, Mail Stop K8-88, Richland, WA 99532; National Institute of Standards and Technology, Gaithersburg, MD 20899High resolution (0.001 cm) coherent anti-Stokes Raman spectroscopy (CARS) was used to directly examine the symmetric stretching mode of the D molecules BF and BF. Calculated spectra were constructed using rovibrational parameters deduced from published infrared hot band, combination band, and difference band studies, and the similarity to the experimental CARS spectra confirms the validity of the constants. No significant perturbations by Fermi resonance or Coriolis interactions with nearby states are observed, in marked contrast to the case of sulfur trioxide, a similar D molecule recently studied. Since the boron nucleus is at the center of mass, the BF and BF Q-branches are the same according to the harmonic oscillator model. Interestingly, the observed frequency of BF is 0.198 cm higher than that of BF. This result is reproduced almost exactly (0.200 cm) using {\it ab initio} calculations (B3LYP/cc-pVTZ) that included evaluation of cubic and quartic force constants and x anharmonicity constants. {\it Ab initio} methods also predict to within 1\% the B and C changes in the rotational constants in going from the ground state to the v = 1 vibrational level
The Charitable Work of Eleanor Clark in the 1850s and the 1870s:Quaker Women's Networks, Sisters and Philanthropy
No full textThis essay is a version of a paper delivered at the Annual Conference for Quaker Historians and Archivists in 2016. It concerns the diverse philanthropic and anti-slavery work of Eleanor Stephens Clark (1812-1879), the Quaker wife of James, the shoemaking pioneer and founder of Clark’s Shoes in Street, in Somerset, in the west country of England. Although much has been written about Clarks’ shoes, far less has been published on the activities of Eleanor Clark. Thus this essay directs attention to a lesser-known Quaker woman, and reinforces the idea that influential women were often invisible in the nineteenth century. Using archival evidence in the Library of the Religious Society of Friends in London, the Alfred Gillett Trust in Street and the Library of Haverford College, Philadelphia, the essay outlines some of Clark’s charitable, humanitarian and anti-slavery activities in the 1850s and the 1870s. It explains the important, but hitherto unknown, place that Eleanor held within a number of female Quaker networks linking women across the UK and USA. These operated as efficient, interconnected webs, connecting large numbers and multiple, charitable and practical humanitarian campaigns. It begins with a brief introduction to the ‘Penny Offering’, a collection to raise funds for Harriet Beecher Stowe, author of Uncle Tom’s Cabin (1852). Instigated by Hannah Sturge, Eleanor’s close friend at the Birmingham Ladies’ Negro’s Friend Society (Britain’s largest female anti-slavery society), the Penny Offering achieved national importance. The essay then outlines the ‘Weims Campaign’, a manumission drive to free John Weims and his enslaved family, as instigated by Quaker kinswoman Anna Richardson of Newcastle. The essay focuses on the ‘Street Olive Leaf Society’ or ‘Circle’, set up in the village of Street by Eleanor, and one of a network of 150 all-female societies across the UK. Founded by New England activist Elihu Burritt, Clark and her kinswomen or ‘League Sisters’ met monthly, primarily to sew goods for ‘Grand Charity Bazaars’, in order to provide funds for Burritt’s League of Brotherhood, a global peace network, promoted by Quakers in commerce and industry. The League also campaigned vigorously for the anti-slavery movement, its angle being that slavery could be defeated via consumer boycotts of slave-made goods and their replacement with ‘free produce’ alternatives – this was emphatically the domain of female consumers. In addition to the UK, some crafted items were directed to anti-slavery fairs in America. Printed flyers provide insights into taste and commerce within Quaker philanthropy at the time; a rich melange of ‘most saleable’ goods such as ‘Plain and fancy needlework … Clothing for the Poor … dressed dolls … Relics of Antiquity … marmalade and articles for the work box, desk and dressing case.’ All ages were encouraged to make items; daughters used the opportunity as training in sewing techniques. In addition, the Olive Leaf Society had an educational remit through its publication, The Olive Leaf or Peace Magazine for the Young. Editions included illustrated essays by female authors, on for example, the wickedness of greed and cruelty to slaves and the importance of peace, charity, plain clothing and Temperance. Aimed at family and ‘Sabbath’ readership, they had an emotive appeal. Whilst being under the radar of public scrutiny, the Olive Leaf Society and its activities facilitated women’s influence in philanthropy and morality; they offered a space through which women could segue between private and public domains, and allowed them to weave together the seemingly conflicting identities of home-maker and tireless campaigner for peace and freedom. Burritt recognised the crucial role of the huge body of ‘Sisters’ that were mobilised and he inspired a loyal following among them. Whilst not permitted full membership of the League, it was through fundraising that women found public, active, autonomous and influential roles. The final part of the essay moves to charity directed towards freed African Americans, following the Civil War. ‘Freedmen’s Aid Societies’ proliferated in the UK in the 1860s, but as Clare Midgley points out; ‘Only a handful of activists maintained an interest in the plight of free blacks after the 1860s.’ Eleanor Clark was part of this tiny minority. Until her death in 1879, assisted by her daughter Sophia Sturge Clark, Eleanor collected donations of clothing and textiles to ship to Kansas, where numbers of ex-enslaved had gathered. The so-called ‘Exodus’ saw destitution and starvation among the migrants; a plight that the Clarks could not ignore. This reinforces Eleanor Clark’s commitment to charitable works, and the continuum of philanthropy that was passed from mother to daughter. <br/
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High-resolution infrared studies of the ν10, ν11, ν14, and ν18 levels of [1.1.1]propellane
No full textThis paper is a continuation of earlier work in which the high resolution infrared spectrum of [1.1.1]propellane was measured and its k and l structure resolved for the first time. Here we present results from an analysis of more than 16,000 transitions involving three fundamental bands v₁₀ (E' - A'₁), v₁₁ (E' - A'₁), v₁₄ (A"₂ - A'₁) and two difference bands (v₁₀–v₁₈) (E' - E") and (v₁₁ - v₁₈) (E' - E"). Additional information about v₁₈ was also obtained from the difference band (v₁₅ + v₁₈) - v₁₈ (E' - E") and the binary combination band (v₁₅ + v₁₈) (E' - A'₁). Through the use of the ground state constants reported in an earlier paper [1], rovibrational constants have been determined for all the vibrational states involved in these bands. The rovibrational parameters for the v₁₈ (E") state were obtained from combination–differences and showed no need to include interactions with other states. The v₁₀ (E') state analysis was also straight-forward, with only a weak Coriolis interaction with the levels of the v₁₄ (A"₂) state. The latter levels are much more affected by a strong Coriolis interaction with the levels of the nearby v₁₁ (E') state and also by a small but significant interaction with another state, presumably the v₁₆ (E") state, that is not directly observed. Gaussian calculations (B3LYP/cc-pVTZ) computed at the anharmonic level aided the analyses by providing initial values for many of the parameters. These theoretical results generally compare favorably with the final parameter values deduced from the spectral analyses. Finally, evidence was obtained for several level crossings between the rotational levels of the v₁₁ and v₁₄ states and, using a weak coupling term corresponding to a Δk = ±5, Δl = ∓1 matrix element, it was possible to find transitions from the ground state that, combined with transitions to the same upper state, give a value of C₀ = 0.1936515(4) cm⁻¹. This result, combined with the value of B₀ = 0.28755833(14) cm⁻¹ reported earlier [1], yields a value of 1.586277(3) Å for the length of the novel axial CC bond in propellane
Silenced Voices: Hearing Biblical Women Through the Genesis Apocryphon
No full textThe #MeToo movement broke the silence around abuse of women. Within the church, women’s voices have been dismissed, disbelieved, or intimidated into silence, reflecting the Bible’s depiction of women as passive and silent, if mentioned. In stark contrast, a new text found in the Dead Sea Scrolls – called the Genesis Apocryphon – contains a retelling of Genesis stories in which the women are named, identified, and given speech and action. Why did these ancient scribes choose to expand the female characters? This study employs both biblical and feminist studies to examine the four stories of women in the Genesis Apocryphon: the women of the Watchers myth, Batenosh, Emzara, and Sarai. It finds the Second Temple authors expanding female characters’ identities in order to emphasize endogamous marriages. The Genesis Apocryphon’s inclusion of women’s voices illuminates the deafening silence of Genesis and points a way forward for biblical interpretation and feminist praxis today.Dead Sea ScrollsGenesis ApocryphonsilenceGenesisAramaicMeToo Movementwomenendogam
A World of Their Own Making: Student Life at Southern Women’s Colleges, 1800-1865
No full textSince the 1980s, the majority of historical scholarship on southern women’s education has concentrated on seeking answers to the question “to what extent was antebellum southern women’s education an oppressive or liberating force?” While keenly noting that the emergence of women’s higher education in the early nineteenth-century South did not necessarily entail advancement for women,1 much of this existing scholarship, because it is focused on analysing institutional records, looks primarily at college curricula and practices to answer questions regarding the value of education; accordingly, this scholarship concludes that, while women’s higher education was new to the early nineteenth-century South, it did not offer southern women anything “new” in terms of social position and therefore was not ultimately a liberating force. While the existing scholarship is useful because it points out the engendered nature of southern women’s education, an exploration of students’ recollections of their college experiences challenges the conclusion that women’s colleges offered women nothing new and were ultimately oppressive forces. For while women’s college education was engendered in such a way that it aimed to reinforce pre-existing ideas concerning southern womanhood this does not necessarily mean that the ideals of women’s education matched its actual out-workings. Indeed, assuming that the “ideal” matched the “real” ignores female students’ responses to their engendered educations. Paying attention to students’ recollections of their college experiences reveals that the college experience actually granted young women the opportunity to shape their own female-controlled world in the midst of living in an intensely patriarchal society. Perhaps surprisingly, though, the world that these students shaped through their cultivation of academic, social, and religious cultures was one in which they not only challenged the gender ideals of southern society and thereby formed new identities as women, but one in which they also (somewhat paradoxically) upheld a hierarchical structure that undermined any type of sisterhood or collective redefinition of southern womanhood and, at times, even reinforced more traditional gender conventions. Thus, a study of southern women’s colleges that privileges the agency of female students not only provides a more complete picture of women’s education, but highlights the complexity of southern women’s identities and thereby contributes to wider discussions within southern and women’s history
Ecological energetics of Eudyptes penguins at Marion Island
No full textIncludes bibliographies.Macaroni Penguins (Eudyptes chrysolophus) and Rockhopper Penguins (E. chrysocome) breed sympatrically at Marion Island in the sub-Antarctic, where they account for a substantial proportion of the avian biomass breeding at the island. This thesis documents the energy requirements of the two species during their respective breeding and moulting cycles at the island. Resting metabolic rates, calculated from lowest, stable rates of oxygen consumption over 24 h, averaged 25 % greater than basal metabolic rates predicted from allometric equations. Body temperatures of the penguins and the relationships between metabolic rates and temperature were investigated over a range of -10°C to 25°C. Lower critical temperature of Rockhopper Penguins was between 0°C and 5°C, but that of Macaroni Penguins could not be clearly ascertained. Measured metabolic rates of other species of penguins are reviewed and intra- and inter-specific differences in metabolic rates are discussed. In contrast to most penguins measured, individuals maintained in zoos or held in captivity for long periods had metabolic rates lower than predicted basal levels
