Geometric bonding effects in the X2A1, A2∑+u, and B2IIg states of Li2F

Published ab-initio and pseudopotential calculations for the dialkali halide systems suggest that the preferred co-linear geometry is for the metal to approach the metal end of the alkali halide. Here, ab-initio calculations on the Li2F system reveal that the well depth on the halide side in this radical is much deeper and is a local saddle-point associated with the ionic non-linear global minima. Although many features of the pseudopotential surfaces are confirmed, significant differences are apparent including the existence of a linear excited state instead of a triangular one, a considerably deeper global minimum some 50% lower in energy and a close approach between the X2A1 and the states, with the minimum 87 kJ mol-1 below the ground state asymptote. All the results can be rationalised as the avoided crossings between a long range, covalent potential dominant within the LiLiF geometry and an ionic state that forms the global minimum. Calculations on the 3rd 2A' potential indicate that even for Li + LiF collisions at ultracold temperatures the collision dynamics could involve as many as three electronic states.

Changes in solar activity and Holocene climatic shifts derived from C-14 wiggle-match dated peat deposits

Closely spaced sequences of accelerator mass spectrometer (AMS) C-14 dates of peat deposits display century-scale wiggles which can be fitted to the radiocarbon calibration curve. By wiggle-matching such sequences, high-precision calendar age chronologies can be generated which show that changes in mire surface wetness during the Bronze Age/Iron Age transition (c. 850 cal. BC) and the 'Little Ice Age' (Wolf, Sporer, Maunder and Dalton Minima) occurred during periods of suddenly increasing atmospheric concentration of C-14. Replicate evidence from peat-based proxy climate indicators in northwest Europe suggest these changes in climate may have been driven by temporary declines of solar activity. Carbon-accumulation rates of two raised peat bogs in the UK and Denmark record low values during the 'Little Ice Age' which reflects reduced primary productivity of the peat-forming vegetation during these periods of climatic deterioration.

Incised palaeo-channels of the Late Middle Pleistocene Thames: age, origins and implications for fluvial palaeogeography and sea-level reconstruction in the southern North Sea Basin.

Multidisciplinary investigations of the infills of steeply-incised buried channels on the coast of Essex, England, provide important insights into late Middle Pleistocene climate and sea-level change and have a direct bearing on the differentiation of MIS 11 and MIS 9 in terrestrial records. New data are presented from Rochford and Burnham-on-Crouch where remnants of two substantial palaeo-channels filled with interglacial sediment can be directly related to the terrace stratigraphy of the Thames. The sediments in both channels accumulated in an estuarine environment early in an interglacial when mixed oak forest was becoming established. Lithological evidence suggests that the interglacial beds post-date the brackish-water infill of an older palaeo-channel ascribed to the Hoxnian and correlated with part of MIS 11, and pre-date terrace gravels (Barling Gravel) ascribed to MIS 8. An MIS 9 attribution is supported by molluscan biostratigraphy, palaeo-salinity and amino-acid racemization data. The relative sea-level record in this area thus includes evidence for two major marine transgressions during MIS 11 and MIS 9, with local maxima of >10 m O.D. Both are associated with sediments that show ‘Hoxnian’ palynological affinities. The wider significance of these findings, and of an intermediate phase of pronounced fluvial incision during MIS 10, is discussed.

Approximating the Set of Local Minima in Partial RNA Folding Landscapes

Motivation: We study a stochastic method for approximating the set of local minima in partial RNA folding landscapes associated with a bounded-distance neighbourhood of folding conformations. The conformations are limited to RNA secondary structures without pseudoknots. The method aims at exploring partial energy landscapes pL induced by folding simulations and their underlying neighbourhood relations. It combines an approximation of the number of local optima devised by Garnier and Kallel (2002) with a run-time estimation for identifying sets of local optima established by Reeves and Eremeev (2004).

Results: The method is tested on nine sequences of length between 50 nt and 400 nt, which allows us to compare the results with data generated by RNAsubopt and subsequent barrier tree calculations. On the nine sequences, the method captures on average 92% of local minima with settings designed for a target of 95%. The run-time of the heuristic can be estimated by O(n2D?ln?), where n is the sequence length, ? is the number of local minima in the partial landscape pL under consideration and D is the maximum number of steepest descent steps in attraction basins associated with pL.

Partial and total multiphoton detachment rates for H- in a perturbative B-spline-based approach

An ab initio approach has been applied to study multiphoton detachment rates for the negative hydrogen ion in the lowest nonvanishing order of perturbation theory. The approach is based on the use of B splines allowing an accurate treatment of the electronic repulsion. Total detachment rates have been determined for two- to six-photon processes as well as partial rates for detachment into the different final symmetries. It is shown that B-spline expansions can yield accurate continuum and bound-state wave functions in a very simple manner. The calculated total rates for two- and three-photon detachment are in good agreement with other perturbative calculations. For more than three-photon detachment little information has been available before now. While the total cross sections show little structure, a fair amount of structure is predicted in the partial cross sections. In the two-photon process, it is shown that the detached electrons mainly have s character. For four- and six-photon processes, the contribution from the d channel is the most important. For three- and five-photon processes p electrons dominate the electron emission spectrum. Detachment rates for s and p electrons show minima as a function of photon energy. © 1994 The American Physical Society.

Structure and interactions of ultracold Yb ions and Rb atoms

In order to study ultracold charge-transfer processes in hybrid atom-ion traps, we have mapped out the potential-energy curves and molecular parameters for several low-lying states of the Rb, Yb+ system. We employ both a multireference configuration interaction and a full configuration interaction (FCI) approach. Turning points, crossing points, potential minima, and spectroscopic molecular constants are obtained for the lowest five molecular states. Long-range parameters, including the dispersion coefficients, are estimated from our ab initio data. The separated-atom ionization potentials and atomic polarizability of the ytterbium atom (ad=128.4 atomic units) are in good agreement with experiment and previous calculations. We present some dynamical calculations for (adiabatic) scattering lengths for the two lowest (Yb, Rb+) channels that were carried out in our work. However, we find that the pseudopotential approximation is rather limited in validity and only applies to nK temperatures. The adiabatic scattering lengths for both the triplet and singlet channels indicate that both are large and negative in the FCI approximation.

Late Quaternary glaciations in Far NE Russia; combining moraines, topography and chronology to assess regional and global glaciation synchrony

During various periods of Late Quaternary glaciation, small ice-sheets, -caps, -fields and valley glaciers, occupied the mountains and uplands of Far NE Russia (including the Verkhoyansk, Suntar-Khayata, and Chersky Mountains; the KolymaeAnyuy and Koryak Highlands; and much of the Kamchatka and Chukchi
Peninsulas). Here, the margins of former glaciers across this region are constrained through the comprehensive mapping of moraines from remote sensing data (Landsat 7 ETM+ satellite images; ASTER Global Digital Elevation Model (GDEM2); and Viewfinder Panorama DEM data). A total of 8414 moraines
are mapped, and this record is integrated with a series of published age-estimates (n = 25), considered to chronologically-constrain former ice-margin positions. Geomorphological and chronological data are compiled in a Geographic Information System (GIS) to produce ‘best estimate’ reconstructions of ice extent during the global Last Glacial Maximum (gLGM) and, to a lesser degree, during earlier phases of glaciation. The data reveal that much of Far NE Russia (~1,092,427 km2) preserves a glaciated landscape (i.e. is bounded by moraines), but there is no evidence of former ice masses having extended more than 270 km beyond mountain centres (suggesting that, during the Late Quaternary, the region has not been occupied by extensive ice sheets). During the gLGM, specifically, glaciers occupied ~253,000 km2, and rarely extended more than 50 km in length. During earlier (pre-gLGM) periods, glaciers were more extensive, though the timing of former glaciation, and the maximum Quaternary extent, appears to have been asynchronous across the region, and out-of-phase with ice-extent maxima elsewhere in the Northern Hemisphere. This glacial history is partly explained through consideration of climatic-forcing
(particularly moisture-availability, solar insolation and albedo), though topographic-controls upon the former extent and dynamics of glaciers are also considered, as are topographic-controls upon moraine deposition and preservation. Ultimately, our ability to understand the glacial and climatic history of this region is restricted when the geomorphological-record alone is considered, particularly as directly-dated glacial deposits are few, and topographic and climatic controls upon the moraine record are difficult to
distinguish.

Developing an integrated hydrograph separation and lumped modelling approach to quantifying hydrological pathways in Irish river catchments

An appreciation of the quantity of streamflow derived from the main hydrological pathways involved in transporting diffuse contaminants is critical when addressing a wide range of water resource management issues. In order to assess hydrological pathway contributions to streams, it is necessary to provide feasible upper and lower bounds for flows in each pathway. An important first step in this process is to provide reliable estimates of the slower responding groundwater pathways and subsequently the quicker overland and interflow pathways. This paper investigates the effectiveness of a multi-faceted approach applying different hydrograph separation techniques, supplemented by lumped hydrological modelling, for calculating the Baseflow Index (BFI), for the development of an integrated approach to hydrograph separation. A semi-distributed, lumped and deterministic rainfall runoff model known as NAM has been applied to ten catchments (ranging from 5 to 699 km2). While this modelling approach is useful as a validation method, NAM itself is also an important tool for investigation. These separation techniques provide a large variation in BFI, a difference of 0.741 predicted for BFI in a catchment with the less reliable fixed and sliding interval methods and local minima turning point methods included. This variation is reduced to 0.167 with these methods omitted. The Boughton and Eckhardt algorithms, while quite subjective in their use, provide quick and easily implemented approaches for obtaining physically realistic hydrograph separations. It is observed that while the different separation techniques give varying BFI values for each of the catchments, a recharge coefficient approach developed in Ireland, when applied in conjunction with the Master recession Curve Tabulation method, predict estimates in agreement with those obtained using the NAM model, and these estimates are also consistent with the study catchments’ geology. These two separation methods, in conjunction with the NAM model, were selected to form an integrated approach to assessing BFI in catchments.

Improved description of chemical barriers with generalized gradient approximations (GGAs) and meta-GGAs

The performance of exchange and correlation (xc) functionals of the generalized gradient approximation (GGA) type and of the meta-GGA type in the calculation of chemical reactions is related to topological features of the electron density which, in turn, are connected to the orbital structure of chemical bonds within the Kohn-Sham (KS) theory. Seventeen GGA and meta-GGA xc functionals are assessed for 15 hydrogen abstraction reactions and 3 symmetrical S(N)2 reactions. Systems that are problematic for standard GGAs characteristically have enhanced values of the dimensionless gradient argument s(sigma)(2) with local maxima in the bonding region. The origin of this topological feature is the occupation of valence KS orbitals with an antibonding or essentially nonbonding character. The local enhancement of s(sigma)(2) yields too negative exchange-correlation energies with standard GGAs for the transition state of the S(N)2 reaction, which leads to the reduced calculated reaction barriers. The unwarranted localization of the effective xc hole of the standard GGAs, i.e., the nondynamical correlation that is built into them but is spurious in this case, wields its effect by their s(sigma)(2) dependence. Barriers are improved for xc functionals with the exchange functional OPTX as x component, which has a modified dependence on s(sigma)(2). Standard GGAs also underestimate the barriers for the hydrogen abstraction reactions. In this case the barriers are improved by correlation functionals, such as the Laplacian-dependent (LAP3) functional, which has a modified dependence on the Coulomb correlation of the opposite- and like-spin electrons. The best overall performance is established for the combination OLAP3 of OPTX and LAP3.

Influence of the Pacific Decadal Oscillation, El Niño-Southern Oscillation and solar forcing on climate and primary productivity changes in the northeast Pacific

Evidence of 11-year Schwabe solar sunspot cycles, El Niño-Southern Oscillation (ENSO) and the Pacific Decadal Oscillation (PDO) were detected in an annual record of diatomaceous laminated sediments from anoxic Effingham Inlet, Vancouver Island, British Columbia. Radiometric dating and counting of annual varves dates the sediments from AD 1947-1993. Intact sediment slabs were X-rayed for sediment structure (lamina thickness and composition based on gray-scale), and subsamples were examined for diatom abundances and for grain size. Wavelet analysis reveals the presence of ~2-3, ~4.5, ~7 and ~9-12-year cycles in the diatom record and an w11e13 year record in the sedimentary varve thickness record. These cycle lengths suggest that both ENSO and the sunspot cycle had an influence on primary productivity and sedimentation patterns. Sediment grain size could not be correlated to the sunspot cycle although a peak in the grain size data centered around the mid-1970s may be related to the 1976-1977 Pacific climate shift, which occurred when the PDO index shifted from negative (cool conditions) to positive (warm conditions). Additional evidence of the PDO regime shift is found in wavelet and cross-wavelet results for Skeletonema costatum, a weakly silicified variant of S. costatum, annual precipitation and April to June precipitation. Higher spring (April/May) values of the North Pacific High pressure index during sunspot minima suggest that during this time, increased cloud cover and concomitant suppression of the Aleutian Low (AL) pressure system led to strengthened coastal upwelling and enhanced diatom production earlier in the year. These results suggest that the 11-year solar cycle, amplified by cloud cover and upwelling changes, as well as ENSO, exert significant influence on marine primary productivity in the northeast Pacific. The expression of these cyclic phenomena in the sedimentary record were in turn modulated by the phase of PDO, as indicated by the change in period of ENSO and suppression of the solar signal in the record after the 1976-1977 regime shift. © 2013 Elsevier Ltd and INQUA. All rights reserved.

Pleistocene and Holocene glacier fluctuations upon the Kamchatka Peninsula

This review summarises landform records and published age-estimates (largely based upon tephrochronology) to provide an overview of glacier fluctuations upon the Kamchatka Peninsula during the Holocene and, to a lesser degree, earlier phases of glaciation. The evidence suggests that following deglaciation from the Last Glacial Maximum (LGM), the peninsula experienced numerous phases of small-scale glacial advance. During the Late Glacial, moraine sequences appear to reflect the former presence of extensive glaciers in some parts of the peninsula, though little chronological control is available for deposits of this period. During the Holocene, the earliest and most extensive phase of advance likely occurred sometime prior to c. 6.8 ka, when glaciers extended up to 8 km beyond their current margins. However, these deposits lack maximum age constrains, and pre-Holocene ages cannot be discounted. Between c. 6.8 ka and the onset of ‘Neoglaciation’ c. 4.5 ka, there is little evidence of glacial advance upon the peninsula, and this period likely coincides with the Holocene climatic optimum (or ‘hypsithermal’). Since c. 4.5 ka, numerous moraines have been deposited, likely reflecting a series of progressively less extensive phases of ice advance during the Late Holocene. The final stage of notable ice advance occurred during the Little Ice Age (LIA), between c. 1350 and 1850 C.E., when reduced summer insolation in the Northern Hemisphere likely coincided with solar activity minima and several strong tropical volcanic eruptions to induce widespread cooling. Following the LIA, glaciers upon the peninsula have generally shown a pattern of retreat, with accelerated mass loss in recent decades. However, a number of prominent climatically and non-climatically controlled glacial advances have also occurred during this period. In general, there is evidence to suggest that millennial scale patterns in the extent and timing of glaciation upon the peninsula (encompassing much of the last glacial period) are governed by the extent of ice sheets in North America. Millennial-to-centennial scale fluctuations of Kamchatkan glaciers (encompassing much of the Holocene) are governed by the location and relative intensity of the Aleutian Low and Siberian High pressure systems. Decadal scale variations in glacier extent and mass balance (particularly since the LIA) are governed by inter-decadal climatic variability over the North Pacific (as reflected by the Pacific Decadal Oscillation), alongside a broader trend of hemispheric warming.

Ion-acoustic supersolitons in plasmas with two-temperature electrons: Boltzmann and kappa distributions

Acoustic supersolitons arise when a plasma model is able to support three consecutive local extrema of the Sagdeev pseudopotential between the undisturbed conditions and an accessible root. This leads to a characteristic electric field signature, where a simple bipolar shape is enriched by subsidiary maxima. Large-amplitude nonlinear acoustic modes are investigated, using a pseudopotential approach, for plasmas containing two-temperature electrons having Boltzmann or kappa distributions, in the presence of cold fluid ions. The existence domains for positive supersolitons are derived in a methodological way, both for structure velocities and amplitudes, in terms of plasma compositional parameters. In addition, typical pseudopotentials, soliton, and electric field profiles have been given to illustrate that positive supersolitons can be found in the whole range of electron distributions from Maxwellian to a very hard nonthermal spectrum in kappa. However, it is found that the parameter ranges that support supersolitons vary significantly over the wide range of kappa considered. VC 2013 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4818888]

Rapid rise in Effective Sea-Level in southwest Bangladesh: Its causes and contemporary rates

Evidence is presented from three estuarine tide gauges located in the
Sundarban area of southwest Bangladesh of relative sea level rise
substantially in excess of the generally accepted rates from altimetry, as
well as previous tide-gauge analyses. It is proposed that the difference
arises from the use of relative mean sea level (RMSL) to characterise the
present and future coastal flood hazard, since RMSL can be misleading in
estuaries in which tidal range is changing. Three tide gauges, one located in
the uninhabited mangrove forested area (Sundarban) of southwest
Bangladesh, the others in the densely populated polder zone north of the
present Sundarban, show rates of increase in RMSL ranging from 2.8 mm
a-1 to 8.8 mm a-1. However, these trends in RMSL disguise the fact that high
water levels in the polder zone have been increasing at an average rate of
15.9 mm a-1 and a maximum of 17.2 mm a-1. In an area experiencing tidal
range amplification, RMSL will always underestimate the rise in high water
levels; consequently, as an alternative to RMSL, the use of trends in high
water maxima or ‘Effective Sea Level Rise’ (ESLR) is adopted as a more
strategic parameter to characterise the flooding hazard potential. The rate
of increase in ESLR is shown to be due to a combination of deltaic
subsidence, including sediment compaction, and eustatic sea level rise, but
principally as a result of increased tidal range in estuary channels recently
constricted by embankments. These increases in ESLR have been partially
offset by decreases in fresh water discharge in those estuaries connected
to the Ganges. The recognition of increases of the effective sea level in the
Bangladesh Sundarban, which are substantially greater than increases in
mean sea level, is of the utmost importance to flood management in this
low-lying and densely populated area.

Long-term mass balance of perennial firn and ice in an Alpine cave (Austria):Constraints from radiocarbon-dated wood fragments

Hundsalm ice cave located at 1520 m altitude in a karst region of western Austria contains up to 7-m-thick deposits of snow, firn and congelation ice. Wood fragments exposed in the lower parts of an ice and firn wall were radiocarbon accelerator mass spectrometry (AMS) dated. Although the local stratigraphy is complex, the 19 individual dates - the largest currently available radiocarbon dataset for an Alpine ice cave - allow to place constraints on the accumulation and ablation history of the cave ice. Most of the cave was either ice free or contained only a small firn and ice body during the 'Roman Warm Period'; dates of three wood fragments mark the onset of firn and ice build-up in the 6th and 7th century ad. In the central part of the cave, the oldest samples date back to the 13th century and record ice growth coeval with the onset of the 'Little Ice Age'. The majority of the ice and firn deposit, albeit compromised by a disturbed stratigraphy, appears to have been formed during the subsequent centuries, supported by wood samples from the 15th to the 17th century. The oldest wood remains found so far inside the ice is from the end of the Bronze Age and implies that local relics of prehistoric ice may be preserved in this cave. The wood record from Hundsalm ice cave shows parallels to the Alpine glacier history of the last three millennia, for example, the lack of preserved wood remains during periods of known glacier minima, and underscores the potential of firn and ice in karst cavities as a long-term palaeoclimate archive, which has been degrading at an alarming rate in recent years. © The Author(s) 2013.

Further evidence for cryptic north-western refugia in Europe? Mitochondrial phylogeography of the sibling species Pipistrellus pipistrellus and Pipistrellus pygmaeus

The geographic ranges of European plants and animals underwent periods of contraction and re-colonisation during the climatic oscillations of the Pleistocene. The southern Mediterranean peninsulas (Iberian, Italian and Balkan) have been considered the most likely refugia for temperate/warm adapted species. Recent studies however have revealed the existence of extra-Mediterranean refugia, including the existence of cryptic north-west European refugia during the Last Glacial Maxima (24-14.6 kyr BP). In this study we elucidated the phylogeographic history of two sibling bat species, Pipistrellus pipistrellus and P. pygmaeus in their western European range. We sequenced the highly variable mtDNA D-loop for 167 samples of P. pipistrellus (n = 99) and P. pygmaeus (n = 68) and combined our data with published sequences from 331 individuals. Using phylogenetic methodologies we assessed their biogeographic history. Our data support a single eastern European origin for populations of P. pygmaeus s.str., yet multiple splits and origins for populations of P. pipistrellus s.str., including evidence for refugia within refugia and potential cryptic refugia in north western Europe and in the Caucasus. This complex pattern in the distribution of mtDNA haplotypes supports a long history for P. pipistrellus s.str. in Europe, and the hypothesis that species with a broad ecological niche may have adapted and survived outside southern peninsula throughout the LGM.