Polyatomic molecular Dirac-Hartree-Fock calculations with Gaussian basis sets

Numerical methods have been used successfully in atomic Dirac-Hartree-Fock (DHF) calculations for many years. Some DHF calculations using numerical methods have been done on diatomic molecules, but while these serve a useful purpose for calibration, the computational effort in extending this approach to polyatomic molecules is prohibitive. An alternative more in line with traditional quantum chemistry is to use an analytical basis set expansion of the wave function. This approach fell into disrepute in the early 1980's due to problems with variational collapse and intruder states, but has recently been put on firm theoretical foundations. In particular, the problems of variational collapse are well understood, and prescriptions for avoiding the most serious failures have been developed. Consequently, it is now possible to develop reliable molecular programs using basis set methods. This paper describes such a program and reports results of test calculations to demonstrate the convergence and stability of the method

All-electron molecular Dirac-Hartree-Fock calculations: The group 4 tetrahydrides CH4, SiH4, GeH4, SnH4 and PbH4

A basis-set-expansion Dirac-Hartree-Fock program for molecules is described. Bond lengths and harmonic frequencies are presented for the ground states of the group 4 tetrahydrides, CH4, SiH4, GeH4, SnH4, and PbH4. The results are compared with relativistic effective core potential (RECP) calculations, first-order perturbation theory (PT) calculations and with experimental data. The bond lengths are well predicted by first-order perturbation theory for all molecules, but non of the RECP's considered provides a consistent prediction. Perturbation theory overestimates the relativistic correction to the harmonic frequencies; the RECP calculations underestimate the correction

Adaptation to hummingbird pollination is associated with reduced diversification in Penstemon

This work is licensed under a Creative Commons Attribution 4.0 International License.A striking characteristic of the Western North American flora is the repeated evolution of hummingbird pollination from insect‐pollinated ancestors. This pattern has received extensive attention as an opportunity to study repeated trait evolution as well as potential constraints on evolutionary reversibility, with little attention focused on the impact of these transitions on species diversification rates. Yet traits conferring adaptation to divergent pollinators potentially impact speciation and extinction rates, because pollinators facilitate plant reproduction and specify mating patterns between flowering plants. Here, we examine macroevolutionary processes affecting floral pollination syndrome diversity in the largest North American genus of flowering plants, Penstemon. Within Penstemon, transitions from ancestral bee‐adapted flowers to hummingbird‐adapted flowers have frequently occurred, although hummingbird‐adapted species are rare overall within the genus. We inferred macroevolutionary transition and state‐dependent diversification rates and found that transitions from ancestral bee‐adapted flowers to hummingbird‐adapted flowers are associated with reduced net diversification rate, a finding based on an estimated 17 origins of hummingbird pollination in our sample. Although this finding is congruent with hypotheses that hummingbird adaptation in North American Flora is associated with reduced species diversification rates, it contrasts with studies of neotropical plant families where hummingbird pollination has been associated with increased species diversification. We further used the estimated macroevolutionary rates to predict the expected pattern of floral diversity within Penstemon over time, assuming stable diversification and transition rates. Under these assumptions, we find that hummingbird‐adapted species are expected to remain rare due to their reduced diversification rates. In fact, current floral diversity in the sampled Penstemon lineage, where less than one‐fifth of species are hummingbird adapted, is consistent with predicted levels of diversity under stable macroevolutionary rates

Aquatic community response to volcanic eruptions on the Ecuadorian Andean flank: evidence from the palaeoecological record

Aquatic ecosystems in the tropical Andes are under increasing pressure from human modification of the landscape (deforestation and dams) and climatic change (increase of extreme events and 1.5 °C on average temperatures are projected for AD 2100). However, the resilience of these ecosystems to perturbations is poorly understood. Here we use a multi-proxy palaeoecological approach to assess the response of aquatic ecosystems to a major mechanism for natural disturbance, volcanic ash deposition. Specifically, we present data from two Neotropical lakes located on the eastern Andean flank of Ecuador. Laguna Pindo (1°27.132′S–78°04.847′W) is a tectonically formed closed basin surrounded by a dense mid-elevation forest, whereas Laguna Baños (0°19.328′S–78°09.175′W) is a glacially formed lake with an inflow and outflow in high Andean Páramo grasslands. In each lake we examined the dynamics of chironomids and other aquatic and semi-aquatic organisms to explore the effect of thick (> 5 cm) volcanic deposits on the aquatic communities in these two systems with different catchment features. In both lakes past volcanic ash deposition was evident from four large tephras dated to c.850 cal year BP (Pindo), and 4600, 3600 and 1500 cal year BP (Baños). Examination of the chironomid and aquatic assemblages before and after the ash depositions revealed no shift in composition at Pindo, but a major change at Baños occurred after the last event around 1500 cal year BP. Chironomids at Baños changed from an assemblage dominated by Pseudochironomus and Polypedilum nubifer-type to Cricotopus/Paratrichocladius type-II, and such a dominance lasted for approximately 380 years. We suggest that, despite potential changes in the water chemistry, the major effect on the chironomid community resulted from the thickness of the tephra being deposited, which acted to shallow the water body beyond a depth threshold. Changes in the aquatic flora and fauna at the base of the trophic chain can promote cascade effects that may deteriorate the ecosystem, especially when already influenced by human activities, such as deforestation and dams, which is frequent in the high Andes

Revealing the last 13,500 years of environmental history from the multiproxy record of a mountain lake (Lago Enol, northern Iberian Peninsula)

This is the author's accepted manuscript. The final publication is available at Springer via http://dx.doi.org/10.1007/s10933-009-9387-7.We present the Holocene sequence from Lago Enol (43°16′N, 4°59′W, 1,070 m a.s.l.), Cantabrian Mountains, northern Spain. A multiproxy analysis provided comprehensive information about regional humidity and temperature changes. The analysis included sedimentological descriptions, physical properties, organic carbon and carbonate content, mineralogy and geochemical composition together with biological proxies including diatom and ostracod assemblages. A detailed pollen study enabled reconstruction of variations in vegetation cover, which were interpreted in the context of climate changes and human impact. Four distinct stages were recognized for the last 13,500 years: (1) a cold and dry episode that includes the Younger Dryas event (13,500–11,600 cal. year BP); (2) a humid and warmer period characterizing the onset of the Holocene (11,600–8,700 cal. year BP); (3) a tendency toward a drier climate during the middle Holocene (8,700–4,650 cal. year BP); and (4) a return to humid conditions following landscape modification by human activity (pastoral activities, deforestation) in the late Holocene (4,650–2,200 cal. year BP). Superimposed on relatively stable landscape conditions (e.g. maintenance of well established forests), the typical environmental variability of the southern European region is observed at this site.The Spanish Inter-Ministry Commission of Science and Technology (CICYT), the Spanish National Parks agency, the European Commission, the Spanish Ministry of Science, and the European Social Fund

Revealing the last 13,500 years of environmental history from the multiproxy record of a mountain lake (Lago Enol, northern Iberian Peninsula)

This is the author's accepted manuscript. The final publication is available at Springer via http://dx.doi.org/10.1007/s10933-009-9387-7.We present the Holocene sequence from Lago Enol (43°16′N, 4°59′W, 1,070 m a.s.l.), Cantabrian Mountains, northern Spain. A multiproxy analysis provided comprehensive information about regional humidity and temperature changes. The analysis included sedimentological descriptions, physical properties, organic carbon and carbonate content, mineralogy and geochemical composition together with biological proxies including diatom and ostracod assemblages. A detailed pollen study enabled reconstruction of variations in vegetation cover, which were interpreted in the context of climate changes and human impact. Four distinct stages were recognized for the last 13,500 years: (1) a cold and dry episode that includes the Younger Dryas event (13,500–11,600 cal. year BP); (2) a humid and warmer period characterizing the onset of the Holocene (11,600–8,700 cal. year BP); (3) a tendency toward a drier climate during the middle Holocene (8,700–4,650 cal. year BP); and (4) a return to humid conditions following landscape modification by human activity (pastoral activities, deforestation) in the late Holocene (4,650–2,200 cal. year BP). Superimposed on relatively stable landscape conditions (e.g. maintenance of well established forests), the typical environmental variability of the southern European region is observed at this site.The Spanish Inter-Ministry Commission of Science and Technology (CICYT), the Spanish National Parks agency, the European Commission, the Spanish Ministry of Science, and the European Social Fund

Late-Holocene climatic variability south of the Alps as recorded by lake-level fluctuations at Lake Ledro, Trentino, Italy

International audienceA lake-level record for the late Holocene at Lake Ledro (Trentino, northeastern Italy) is presented. It is based on the sediment and pollen analysis of a 1.75 m high stratigraphic section observed on the southern shore (site Ledro I) and a 3.2 m long sediment core taken from a littoral mire on the southeastern shore (site Ledro II). The chronology is derived from 15 radiocarbon dates and pollen stratigraphy. The late-Holocene composite record established from these two sediment sequences gives evidence of centennial-scale fluctuations with highstands at c. 3400, 2600, 1700, 1200 and 400 cal. BP, in agreement with various palaeohydro-logical records established in central and northern Italy, as well as north of the Alps. In addition, high lake-level conditions at c. 2000 cal. BP may be the equivalent of stronger river discharge observed at the same time in Central Italy's rivers. In agreement with the lake-level record of Accesa (Tuscany), the Ledro record also suggests a relatively complex palaeohydrological pattern for the period around 4000 cal. BP. On a millennial scale, sediment hiatuses observed in the lower part of the Ledro I sediment sequence indicate that, except for a high-stand occurring just after 7500 cal. BP, lower lake levels generally prevailed rather before c. 4000 cal. BP than afterwards. Finally, the lake-level data obtained at Lake Ledro indicate that the relative continuity of settlements in humid areas of northern Italy during the Bronze Age (in contrast to their general abandonment north of the Alps between c. 3450 and 3150 cal. BP), does not reflect different regional patterns of climatic and palaeohy-drological conditions. In contrast, the rise in lake level dated to c. 3400 cal. BP at Ledro appears to coincide with a worldwide climate reversal, observed in both the hemispheres, while palaeoenvironmental and archaeological data collected at Lake Ledro may suggest, as a working hypothesis, a relative emancipation of proto-historic societies from climatic conditions

How the west was once: vegetation change in south-west Queensland from 1930 to 1995

Conflicting perceptions of past and present rangeland condition and limited historical data have led to debate regarding the management of vegetation in pastoral landscapes both internationally and in Australia. In light of this controversy we have sought to provide empirical evidence to determine the trajectory of vegetational change in a semi-arid rangeland for a significant portion of the 20th century using a suite of proxy measures. Ambathala Station, approximately 780 km west of Brisbane, in the semi-arid rangelands of south-western Queensland, Australia. We excavated stratified deposits of sheep manure which had accumulated beneath a shearing shed between the years 1930 and 1995. Multi-proxy data, including pollen and leaf cuticle analyses and analysis of historical aerial photography were coupled with a fine resolution radiocarbon chronology to generate a near annual history of vegetation on the property and local area. Aerial photography indicates that minor (< 5%) increases in the density of woody vegetation took place between 1951 and 1994 in two thirds of the study area not subjected to clearing. Areas that were selectively or entirely cleared prior to the 1950s (approximately 16% of the study area) had recovered to almost 60% of their original cover by the 1994 photo period. This slight thickening is only partially evident from pollen and leaf cuticle analyses of sheep faeces. Very little change in vegetation is revealed over the nearly 65 years based on the relative abundances of pollen taxonomic groups. Microhistological examination of sheep faeces provides evidence of dramatic changes in sheep diet. The majority of dietary changes are associated with climatic events of sustained above-average rainfall or persistent drought. Most notable in the dietary analysis is the absence of grass during the first two decades of the record. In contrast to prevailing perceptions and limited research into long-term vegetation change in the semi-arid areas of eastern Australia, the record of vegetation change at the Ambathala shearing shed indicates only a minor increase in woody vegetation cover and no decrease in grass cover on the property over the 65 years of pastoral activity covered by the study. However, there are marked changes in the abundance of grass cuticles in sheep faeces. The appearance and persistence of grass in sheep diets from the late 1940s can be attributed to the effects of periods of high rainfall and possibly some clearing and thinning of vegetation. Lower stock numbers may have allowed grass to persist through later drought years. The relative abundances of major groups of plant pollen have not changed significantly over the past 65 years

Extremely Long-Lived Stigmas Allow Extended Cross-Pollination Opportunities in a High Andean Plant

High-elevation ecosystems are traditionally viewed as environments in which predominantly autogamous breeding systems should be selected because of the limited pollinator availability. Chaetanthera renifolia (Asteraceae) is an endemic monocarpic triennial herb restricted to a narrow altitudinal range within the high Andes of central Chile (3300–3500 m a.s.l.), just below the vegetation limit. This species displays one of the larger capitulum within the genus. Under the reproductive assurance hypothesis, and considering its short longevity (monocarpic triennial), an autogamous breeding system and low levels of pollen limitation would be predicted for C. renifolia. In contrast, considering its large floral size, a xenogamous breeding system, and significant levels of pollen limitation could be expected. In addition, the increased pollination probability hypothesis predicts prolonged stigma longevity for high alpine plants. We tested these alternative predictions by performing experimental crossings in the field to establish the breeding system and to measure the magnitude of pollen limitation in two populations of C. renifolia. In addition, we measured the stigma longevity in unpollinated and open pollinated capitula, and pollinator visitation rates in the field. We found low levels of self-compatibility and significant levels of pollen limitation in C. renifolia. Pollinator visitation rates were moderate (0.047–0.079 visits per capitulum per 30 min). Although pollinator visitation rate significantly differed between populations, they were not translated into differences in achene output. Finally, C. renifolia stigma longevity of unpollinated plants was extremely long and significantly higher than that of open pollinated plants (26.3±2.8 days vs. 10.1±2.2, respectively), which gives support to the increased pollination probability hypothesis for high-elevation flowering plants. Our results add to a growing number of studies that show that xenogamous breeding systems and mechanisms to increase pollination opportunities can be selected in high-elevation ecosystems