Benchmark Structures and Binding Energies of Small Water Clusters with Anharmonicity Corrections

For (H2O)n where n = 1–10, we used a scheme combining molecular dynamics sampling with high level ab initio calculations to locate the global and many low lying local minima for each cluster. For each isomer, we extrapolated the RI-MP2 energies to their complete basis set limit, included a CCSD(T) correction using a smaller basis set and added finite temperature corrections within the rigid-rotor-harmonic-oscillator (RRHO) model using scaled and unscaled harmonic vibrational frequencies. The vibrational scaling factors were determined specifically for water clusters by comparing harmonic frequencies with VPT2 fundamental frequencies. We find the CCSD(T) correction to the RI-MP2 binding energy to be small (<1%) but still important in determining accurate conformational energies. Anharmonic corrections are found to be non-negligble; they do not alter the energetic ordering of isomers, but they do lower the free energies of formation of the water clusters by as much as 4 kcal/mol at 298.15 K.

Benchmark Structures and Binding Energies of Small Water Clusters with Anharmonicity Corrections

For (H2O)n where n = 1–10, we used a scheme combining molecular dynamics sampling with high level ab initio calculations to locate the global and many low lying local minima for each cluster. For each isomer, we extrapolated the RI-MP2 energies to their complete basis set limit, included a CCSD(T) correction using a smaller basis set and added finite temperature corrections within the rigid-rotor-harmonic-oscillator (RRHO) model using scaled and unscaled harmonic vibrational frequencies. The vibrational scaling factors were determined specifically for water clusters by comparing harmonic frequencies with VPT2 fundamental frequencies. We find the CCSD(T) correction to the RI-MP2 binding energy to be small (

Quantum-Mechanical Investigation of Large Water Clusters

The PM3 quantum-mechanical method has been used to study large water clusters ranging from 8 to 42 water molecules. These large clusters are built from smaller building blocks. The building blocks include cyclic tetramers, pentamers, octamers, and a pentagonal dodecahedron cage. The correlations between the strain energy resulting from bending of the hydrogen bonds formed by different cluster motifs and the number of waters involved in the cluster are discussed. The PM3 results are compared with TIP4P potential and ab initio results. The number of net hydrogen bonds per water increases with the cluster size. This places a limit on the size of clusters that would fit the Benson model of liquid water. Many of the 20-mer clusters fit the Benson model well. Calculations of the ion cluster (H20)4o(H30+)2 reveal that the m/e ratio obtainable by mass spectrometry experiments can uniquely indicate the conformation of the 20 water pentagonal dodecahedron cage present in the larger clusters.

Structures of Cage, Prism, and Book Isomers of Water Hexamer from Broadband Rotational Spectroscopy

Theory predicts the water hexamer to be the smallest water cluster with a three-dimensional hydrogen-bonding network as its minimum energy structure. There are several possible low-energy isomers, and calculations with different methods and basis sets assign them different relative stabilities. Previous experimental work has provided evidence for the cage, book, and cyclic isomers, but no experiment has identified multiple coexisting structures. Here, we report that broadband rotational spectroscopy in a pulsed supersonic expansion unambiguously identifies all three isomers; we determined their oxygen framework structures by means of oxygen-18–substituted water (H218O). Relative isomer populations at different expansion conditions establish that the cage isomer is the minimum energy structure. Rotational spectra consistent with predicted heptamer and nonamer structures have also been identified.

Yolk Androstenedione in Domestic Chicks (Gallus Gallus Domesticus): Uptake and Sex-Dependent Alteration of Growth and Behavior

In birds, causes and consequences of variation in maternally-derived steroids in egg yolk have been the subject of intense experimentation. Many studies have quantified or manipulated testosterone ("T") and one of its immediate precursors, androstenedione ("A4") - often lumping the two steroids as "androgens" and treating them as functionally equivalent. However, yolk A4 is deposited in substantially higher concentrations than T, binds only weakly to the androgen receptor, and is readily converted into either T or estrone by steroidogenic enzymes present during embryonic development. Thus it may not be appropriate to assume that A4 has the same effect as T. In addition, A4's metabolic fate is likely to differ between females and males. The goals of this study were to examine the sex-specific uptake and metabolism of yolk A4 and consequences of elevated levels of yolk A4 on development and behavior of domestic chicks. Eggs were injected with 2mu Ci of tritiated androstenedione; radioactivity was detected in all tissues of day 7 and day 16 embryos and found in both aqueous and organics phases of day 7 yolk, with no difference between sexes. A second set of eggs was injected with 125ng of A4. A4 increased growth of morphological traits (tarsus, beak) in females, but not males. A4 males had smaller combs than controls; there was no treatment effect in females. A4 reduced tonic immobility behavior in both sexes. The results of this study illustrate the importance of distinguishing both between androgens and between sexes when investigating avian endocrine maternal effects. Copyright 2013 Elsevier Inc. All rights reserved.

Age, Sex, and Telomere Dynamics in a Long-Lived Seabird with Male-Biased Parental Care

The examination of telomere dynamics is a recent technique in ecology for assessing physiological state and age-related traits from individuals of unknown age. Telomeres shorten with age in most species and are expected to reflect physiological state, reproductive investment, and chronological age. Loss of telomere length is used as an indicator of biological aging, as this detrimental deterioration is associated with lowered survival. Lifespan dimorphism and more rapid senescence in the larger, shorter-lived sex are predicted in species with sexual size dimorphism, however, little is known about the effects of behavioral dimorphism on senescence and life history traits in species with sexual monomorphism. Here we compare telomere dynamics of thick-billed murres (Uria lomvia), a species with male-biased parental care, in two ways: 1) cross-sectionally in birds of known-age (0-28 years) from one colony and 2) longitudinally in birds from four colonies. Telomere dynamics are compared using three measures: the telomere restriction fragment (TRF), a lower window of TRF (TOE), and qPCR. All showed age-related shortening of telomeres, but the TRF measure also indicated that adult female murres have shorter telomere length than adult males, consistent with sex-specific patterns of ageing. Adult males had longer telomeres than adult females on all colonies examined, but chick telomere length did not differ by sex. Additionally, inter-annual telomere changes may be related to environmental conditions; birds from a potentially low quality colony lost telomeres, while those at more hospitable colonies maintained telomere length. We conclude that sex-specific patterns of telomere loss exist in the sexually monomorphic thick-billed murre but are likely to occur between fledging and recruitment. Longer telomeres in males may be related to their homogamous sex chromosomes (ZZ) or to selection for longer life in the care-giving sex. Environmental conditions appeared to be the primary drivers of annual changes in adult birds.

Monitoring Stormwater Redistribution Into Low Resistivity Soils Using Noninvasive Geophysical Techniques

Water held in the unsaturated zone is important for agriculture and construction and is replenished by infiltrating rainwater. Monitoring the soil water content of clay soils using ground-penetrating radar (GPR) has not been researched, as clay soils cause attenuation of GPR signal. In this study, GPR common-midpoint soundings (CMPs) are used in the clayey soils of the Miller Run floodplain to monitor changes in the soil water content (SWC) before and after rainfall events. GPR accomplishes this task because increases in water content will increase the dielectric constant of the subsurface material, and decrease the velocity of the GPR wave. Using an empirical relationship between dielectric constant and SWC, the Topp relation, we are able to calculate a SWC from these velocity measurements. Non-invasive electromagnetics, resistivity, and seismic were performed, and from these surveys, the layering at the field site was delineated. EM characterized the horizontal variation of the soil, allowing us to target the most clay rich area. At the CMP location, resistivity indicates the vertical structure of the subsurface consists of a 40 cm thick layer with a resistivity of 100 ohm*m. Between 40 cm and 1.5 m is a layer with a resistivity of 40 ohm*m. The thickness estimates were confirmed with invasive auger and trenching methods away from the CMP location. GPR CMPs were collected relative to a July 2013 and September 2013 storm. The velocity observations from the CMPs had a precision of +/- 0.001 m/ns as assessed by repeat analysis. In the case of both storms, the GPR data showed the expected relationship between the rainstorms and calculated SWC, with the SWC increasing sharply after the rainstorm and decreasing as time passed. We compared these data to auger core samples collected at the same time as the CMPs were taken, and the volumetric analysis of the cores confirmed the trend seen in the GPR, with SWC values between 3 and 5 percent lower than the GPR estimates. Our data shows that we can, with good precision, monitor changes in the SWC of conductive soils in response to rainfall events, despite the attenuation induced by the clay.