Implementation and application of basis set superposition error-correction schemes to the theoretical modeling of weak intermolecular interactions

This thesis deals with the so-called Basis Set Superposition Error (BSSE) from both a methodological and a practical point of view. The purpose of the present thesis is twofold: (a) to contribute step ahead in the correct characterization of weakly bound complexes and, (b) to shed light the understanding of the actual implications of the basis set extension effects in the ab intio calculations and contribute to the BSSE debate. The existing BSSE-correction procedures are deeply analyzed, compared, validated and, if necessary, improved. A new interpretation of the counterpoise (CP) method is used in order to define counterpoise-corrected descriptions of the molecular complexes. This novel point of view allows for a study of the BSSE-effects not only in the interaction energy but also on the potential energy surface and, in general, in any property derived from the molecular energy and its derivatives A program has been developed for the calculation of CP-corrected geometry optimizations and vibrational frequencies, also using several counterpoise schemes for the case of molecular clusters. The method has also been implemented in Gaussian98 revA10 package. The Chemical Hamiltonian Approach (CHA) methodology has been also implemented at the RHF and UHF levels of theory for an arbitrary number interacting systems using an algorithm based on block-diagonal matrices. Along with the methodological development, the effects of the BSSE on the properties of molecular complexes have been discussed in detail. The CP and CHA methodologies are used for the determination of BSSE-corrected molecular complexes properties related to the Potential Energy Surfaces and molecular wavefunction, respectively. First, the behaviour of both BSSE-correction schemes are systematically compared at different levels of theory and basis sets for a number of hydrogen-bonded complexes. The Complete Basis Set (CBS) limit of both uncorrected and CP-corrected molecular properties like stabilization energies and intermolecular distances has also been determined, showing the capital importance of the BSSE correction. Several controversial topics of the BSSE correction are addressed as well. The application of the counterpoise method is applied to internal rotational barriers. The importance of the nuclear relaxation term is also pointed out. The viability of the CP method for dealing with charged complexes and the BSSE effects on the double-well PES blue-shifted hydrogen bonds is also studied in detail. In the case of the molecular clusters the effect of high-order BSSE effects introduced with the hierarchical counterpoise scheme is also determined. The effect of the BSSE on the electron density-related properties is also addressed. The first-order electron density obtained with the CHA/F and CHA/DFT methodologies was used to assess, both graphically and numerically, the redistribution of the charge density upon BSSE-correction. Several tools like the Atoms in Molecules topologycal analysis, density difference maps, Quantum Molecular Similarity, and Chemical Energy Component Analysis were used to deeply analyze, for the first time, the BSSE effects on the electron density of several hydrogen bonded complexes of increasing size. The indirect effect of the BSSE on intermolecular perturbation theory results is also pointed out It is shown that for a BSSE-free SAPT study of hydrogen fluoride clusters, the use of a counterpoise-corrected PES is essential in order to determine the proper molecular geometry to perform the SAPT analysis.

A utilização de transformadas de wavelet e de detrended fluctuation analysis no estudo da microcirculação da pele humana

A Fluxometria por Laser Doppler (LDF) é uma técnica não invasiva usada para medir o fluxo microvascular da pele humana. No fluxo é possível isolar componentes oscilatórias em gamas de frequências características que se encontram relacionadas com as actividades cardíaca, respiratória, miogénica, simpática e metabólica. A LDF permite assim estudar a fisiologia do fluxo sanguíneo. Neste trabalho foram realizadas medições de LDF nos tornozelos de 9 mulheres saudáveis numa situação de restrição à perfusão, usando uma braçadeira nos tornozelos. Os dados foram analisados com Transformada de Wavelet e Detrended Fluctuation Analysis (DFA) de modo a estudar os rácios das amplitudes das componentes de Wavelet e os respectivos expoentes . Estes parâmetros foram comparados nas situações de repouso, de restrição à perfusão e de recuperação após remoção da braçadeira. Observou-se que durante a restrição à perfusão houve um aumento significativo dos rácios de amplitude e dos expoentes a para as componentes cardíaca, respiratória e miogénica, o que pode reflectir vasoconstrição. Os parâmetros da componente metabólica apresentaram uma diminuição que se pode relacionar com variações na libertação de NO por parte do endotélio. Após a libertação da braçadeira, os parâmetros das componentes respiratória, miogénica e metabólica retornaram aos valores iniciais. Aanálise combinada de Wavelet com DFAoferece uma nova visão sobre a regulação do fluxo microvascular.

A literature review of three common balance tests: Electronystagmography, Rotary Chair Testing, and Computerized Dynamic Posturography

This paper discusses the rationale, clinical applications, advantages and disadvantages of three common balance function tests: Electronystagmography (ENG), Rotational Chair Testing (RCT), and Computerized Dynamic Posturography (CDP).

Museos de historia y producción de conocimientos: cuestiones para el debate (Debates)

The article thinks over the role of museums in the construction of scientific and historical representations and as a space that connects the forms of visualizing the past and the construction of historic knowledge. Also analyzes the museum as a setting of tension between the visualization and the generation of scientific or historical knowledge; and between the forms of evoking-representing and the sensitive cognitive processes that it activates in museum audiences. This oscillation takes place in the Museo Paulista.

Identification of Putative Wintering Areas and Ecological Determinants of Population Dynamics of Common House-Martin (Delichon urbicum) and Common Swift (Apus apus) Breeding in Northern Italy

To identify the causes of population decline in migratory birds, researchers must determine the relative influence of environmental changes on population dynamics while the birds are on breeding grounds, wintering grounds, and en route between the two. This is problematic when the wintering areas of specific populations are unknown. Here, we first identified the putative wintering areas of Common House-Martin (Delichon urbicum) and Common Swift (Apus apus) populations breeding in northern Italy as those areas, within the wintering ranges of these species, where the winter Normalized Difference Vegetation Index (NDVI), which may affect winter survival, best predicted annual variation in population indices observed in the breeding grounds in 1992–2009. In these analyses, we controlled for the potentially confounding effects of rainfall in the breeding grounds during the previous year, which may affect reproductive success; the North Atlantic Oscillation Index (NAO), which may account for climatic conditions faced by birds during migration; and the linear and squared term of year, which account for nonlinear population trends. The areas thus identified ranged from Guinea to Nigeria for the Common House-Martin, and were located in southern Ghana for the Common Swift. We then regressed annual population indices on mean NDVI values in the putative wintering areas and on the other variables, and used Bayesian model averaging (BMA) and hierarchical partitioning (HP) of variance to assess their relative contribution to population dynamics. We re-ran all the analyses using NDVI values at different spatial scales, and consistently found that our population of Common House-Martin was primarily affected by spring rainfall (43%–47.7% explained variance) and NDVI (24%–26.9%), while the Common Swift population was primarily affected by the NDVI (22.7%–34.8%). Although these results must be further validated, currently they are the only hypotheses about the wintering grounds of the Italian populations of these species, as no Common House-Martin and Common Swift ringed in Italy have been recovered in their wintering ranges.

The response of tropospheric circulation to perturbations in lower-stratospheric temperature

A multiple regression analysis of the NCEP-NCAR reanalysis dataset shows a response to increased solar activity of a weakening and poleward shift of the subtropical jets. This signal is separable from other influences, such as those of El Nino-Southern Oscillation (ENSO) and the North Atlantic Oscillation (NAO), and is very similar to that seen in previous studies using global circulation models (GCMs) of the effects of an increase in solar spectral irradiance. The response to increased stratospheric (volcanic) aerosol is found in the data to be a weakening and equatorward shift of the jets. The GCM studies of the solar influence also showed an impact on tropospheric mean meridional circulation with a weakening and expansion of the tropical Hadley cells and a poleward shift of the Ferrel cells. To understand the mechanisms whereby the changes in solar irradiance affect tropospheric winds and circulation, experiments have been carried out with a simplified global circulation model. The results show that generic heating of the lower stratosphere tends to weaken the subtropical jets and the tropospheric mean meridional circulations. The positions of the jets, and the extent of the Hadley cells, respond to the distribution of the stratospheric heating, with low-latitude heating forcing them to move poleward, and high-latitude or latitudinally uniform heating forcing them equatorward. The patterns of response are similar to those that are found to be a result of the solar or volcanic influences, respectively, in the data analysis. This demonstrates that perturbations to the heat balance of the lower stratosphere, such as those brought about by solar or volcanic activity, can produce changes in the mean tropospheric circulation, even without any direct forcing below the tropopause.

Serial clustering of extratropical cyclones

The clustering in time (seriality) of extratropical cyclones is responsible for large cumulative insured losses in western Europe, though surprisingly little scientific attention has been given to this important property. This study investigates and quantifies the seriality of extratropical cyclones in the Northern Hemisphere using a point-process approach. A possible mechanism for serial clustering is the time-varying effect of the large-scale flow on individual cyclone tracks. Another mechanism is the generation by one parent cyclone of one or more offspring through secondary cyclogenesis. A long cyclone-track database was constructed for extended October March winters from 1950 to 2003 using 6-h analyses of 850-mb relative vorticity derived from the NCEP NCAR reanalysis. A dispersion statistic based on the varianceto- mean ratio of monthly cyclone counts was used as a measure of clustering. It reveals extensive regions of statistically significant clustering in the European exit region of the North Atlantic storm track and over the central North Pacific. Monthly cyclone counts were regressed on time-varying teleconnection indices with a log-linear Poisson model. Five independent teleconnection patterns were found to be significant factors over Europe: the North Atlantic Oscillation (NAO), the east Atlantic pattern, the Scandinavian pattern, the east Atlantic western Russian pattern, and the polar Eurasian pattern. The NAO alone is not sufficient for explaining the variability of cyclone counts in the North Atlantic region and western Europe. Rate dependence on time-varying teleconnection indices accounts for the variability in monthly cyclone counts, and a cluster process did not need to be invoked.

Sensitivity of the ERA40 reanalysis to the observing system: determination of the global atmospheric circulation from reduced observations

The impact of selected observing systems on the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-yr reanalysis (ERA40) is explored by mimicking observational networks of the past. This is accomplished by systematically removing observations from the present observational data base used by ERA40. The observing systems considered are a surface-based system typical of the period prior to 1945/50, obtained by only retaining the surface observations, a terrestrial-based system typical of the period 1950-1979, obtained by removing all space-based observations, and finally a space-based system, obtained by removing all terrestrial observations except those for surface pressure. Experiments using these different observing systems have been limited to seasonal periods selected from the last 10 yr of ERA40. The results show that the surface-based system has severe limitations in reconstructing the atmospheric state of the upper troposphere and stratosphere. The terrestrial system has major limitations in generating the circulation of the Southern Hemisphere with considerable errors in the position and intensity of individual weather systems. The space-based system is able to analyse the larger-scale aspects of the global atmosphere almost as well as the present observing system but performs less well in analysing the smaller-scale aspects as represented by the vorticity field. Here, terrestrial data such as radiosondes and aircraft observations are of paramount importance. The terrestrial system in the form of a limited number of radiosondes in the tropics is also required to analyse the quasi-biennial oscillation phenomenon in a proper way. The results also show the dominance of the satellite observing system in the Southern Hemisphere. These results all indicate that care is required in using current reanalyses in climate studies due to the large inhomogeneity of the available observations, in particular in time.

Variability of the Atlantic thermohaline circulation described by three-dimensional empirical orthogonal functions

We describe the use of bivariate 3d empirical orthogonal functions (EOFs) in characterising low frequency variability of the Atlantic thermohaline circulation (THC) in the Hadley Centre global climate model, HadCM3. We find that the leading two modes are well correlated with an index of the meridional overturning circulation (MOC) on decadal timescales, with the leading mode alone accounting for 54% of the decadal variance. Episodes of coherent oscillations in the sub-space of the leading EOFs are identified; these episodes are of great interest for the predictability of the THC, and could indicate the existence of different regimes of natural variability. The mechanism identified for the multi-decadal variability is an internal ocean mode, dominated by changes in convection in the Nordic Seas, which lead the changes in the MOC by a few years. Variations in salinity transports from the Arctic and from the North Atlantic are the main feedbacks which control the oscillation. This mode has a weak feedback onto the atmosphere and hence a surface climatic influence. Interestingly, some of these climate impacts lead the changes in the overturning. There are also similarities to observed multi-decadal climate variability.

Enhancement of ENSO variability by a weakened Atlantic thermohaline circulation in a coupled GCM

A coupled ocean–atmosphere general circulation model is used to investigate the modulation of El Niño–Southern Oscillation (ENSO) variability due to a weakened Atlantic thermohaline circulation (THC). The THC weakening is induced by freshwater perturbations in the North Atlantic, and leads to a well-known sea surface temperature dipole and a southward shift of the intertropical convergence zone (ITCZ) in the tropical Atlantic. Through atmospheric teleconnections and local coupled air–sea feedbacks, a meridionally asymmetric mean state change is generated in the eastern equatorial Pacific, corresponding to a weakened annual cycle, and westerly anomalies develop over the central Pacific. The westerly anomalies are associated with anomalous warming of SST, causing an eastward extension of the west Pacific warm pool particularly in August–February, and enhanced precipitation. These and other changes in the mean state lead in turn to an eastward shift of the zonal wind anomalies associated with El Niño events, and a significant increase in ENSO variability. In response to a 1-Sv (1 Sv ≡ 106 m3 s−1) freshwater input in the North Atlantic, the THC slows down rapidly and it weakens by 86% over years 50–100. The Niño-3 index standard deviation increases by 36% during the first 100-yr simulation relative to the control simulation. Further analysis indicates that the weakened THC not only leads to a stronger ENSO variability, but also leads to a stronger asymmetry between El Niño and La Niña events. This study suggests a role for an atmospheric bridge that rapidly conveys the influence of the Atlantic Ocean to the tropical Pacific and indicates that fluctuations of the THC can mediate not only mean climate globally but also modulate interannual variability. The results may contribute to understanding both the multidecadal variability of ENSO activity during the twentieth century and longer time-scale variability of ENSO, as suggested by some paleoclimate records.

A regime-dependent balanced control variable based on potential vorticity

In this paper it is argued that rotational wind is not the best choice of leading control variable for variational data assimilation, and an alternative is suggested and tested. A rotational wind parameter is used in most global variational assimilation systems as a pragmatic way of approximately representing the balanced component of the assimilation increments. In effect, rotational wind is treated as a proxy for potential vorticity, but one that it is potentially not a good choice in flow regimes characterised by small Burger number. This paper reports on an alternative set of control variables which are based around potential vorticity. This gives rise to a new formulation of the background error covariances for the Met Office's variational assimilation system, which leads to flow dependency. It uses similar balance relationships to traditional schemes, but recognises the existence of unbalanced rotational wind which is used with a new anti-balance relationship. The new scheme is described and its performance is evaluated and compared to a traditional scheme using a sample of diagnostics.

The effect of doubled CO2 and model basic state biases on the monsoon-ENSO system. II: Changing ENSO regimes

Integrations of a fully-coupled climate model with and without flux adjustments in the equatorial oceans are performed under 2×CO2 conditions to explore in more detail the impact of increased greenhouse gas forcing on the monsoon-ENSO system. When flux adjustments are used to correct some systematic model biases, ENSO behaviour in the modelled future climate features distinct irregular and periodic (biennial) regimes. Comparison with the observed record yields some consistency with ENSO modes primarily based on air-sea interaction and those dependent on basinwide ocean wave dynamics. Simple theory is also used to draw analogies between the regimes and irregular (stochastically forced) and self-excited oscillations respectively. Periodic behaviour is also found in the Asian-Australian monsoon system, part of an overall biennial tendency of the model under these conditions related to strong monsoon forcing and increased coupling between the Indian and Pacific Oceans. The tropospheric biennial oscillation (TBO) thus serves as a useful descriptor for the coupled monsoon-ENSO system in this case. The presence of obvious regime changes in the monsoon-ENSO system on interdecadal timescales, when using flux adjustments, suggests there may be greater uncertainty in projections of future climate, although further modelling studies are required to confirm the realism and cause of such changes.

Impact of Tibetan Orography and Heating on the Summer Flow over Asia

The influence on the summer flow over Asia of both the orographic and thermal forcing of the Tibetan Plateau is investigated using a sequence of idealised experiments with a global primitive equation model. The zonally averaged flow is prescribed and both realistic and idealised orography and heating are used. There is some similarity between the responses to the two forcings when applied separately. The upper tropospheric Tibetan anticyclone is predominantly forced by the heating but also weakly by the orography. Below this, both forcings tend to give air descending in an equatorward anticyclonic circulation down the isentropes to the west and rising in a similar poleward circulation to the east. However the heating-only response has a strong ascending southwesterly flow that is guided around the south and south-east of the orography when it is included. On the northern side, the westerly flow over the orography gives ascent on the upslope and descent on the downslope. It is found that heating over the Plateau leads to a potential vorticity (PV) minimum and that if it is sufficiently strong the flow is unstable, producing a quasi-biweekly oscillation. During this oscillation the Tibetan anticyclone changes between a single centre over the southwestern side of the Plateau and a split/double structure with centres over China and the Middle East. These characteristics are similar to observed variability in the region. Associated with this quasi-biweekly oscillation are significant variations in the strength of the ascent over the Plateau and the Rossby wave pattern over the North Pacific. The origin of the variability is instability associated with the zonally extended potential vorticity PV minimum on a θ-surface, as proposed by Hsu and Plumb (2000). This minimum is due to the tendency to reduce the PV above the heating over the Plateau and to advection by the consequent anticyclone of high PV around from the east and low PV to the west. The deep convection to the south and southeast of the Plateau tends to suppress the quasi-biweekly oscillation because the low PV produced above it acts to reduce the meridional PV gradient reversal. The occurrence of the oscillation depends on the relative magnitude of the heating in the two regions.

On the natural variability of the pre-industrial European climate

We suggest that climate variability in Europe for the “pre-industrial” period 1500–1900 is fundamentally a consequence of internal fluctuations of the climate system. This is because a model simulation, using fixed pre-industrial forcing, in several important aspects is consistent with recent observational reconstructions at high temporal resolution. This includes extreme warm and cold seasonal events as well as different measures of the decadal to multi-decadal variance. Significant trends of 50-year duration can be seen in the model simulation. While the global temperature is highly correlated with ENSO (El Nino- Southern Oscillation), European seasonal temperature is only weakly correlated with the global temperature broadly consistent with data from ERA-40 reanalyses. Seasonal temperature anomalies of the European land area are largely controlled by the position of the North Atlantic storm tracks. We believe the result is highly relevant for the interpretation of past observational records suggesting that the effect of external forcing appears to be of secondary importance. That variations in the solar irradiation could have been a credible cause of climate variations during the last centuries, as suggested in some previous studies, is presumably due to the fact that the models used in these studies may have underestimated the internal variability of the climate. The general interpretation from this study is that the past climate is just one of many possible realizations and thus in many respects not reproducible in its time evolution with a general circulation model but only reproducible in a statistical sense.

How does a weakened Atlantic thermohaline circulation lead to an intensification of the ENSO-south Asian summer monsoon interaction?

This study investigates the change of the El Niño–Southern Oscillation (ENSO)-South Asian summer monsoon interaction in response to a weakened Atlantic thermohaline circulation (THC) by applying an additional freshwater flux into the North Atlantic. The simulated results indicate that the weakened THC leads to intensified ENSO-South Asian summer monsoon relationship and enhanced South Asian summer monsoon interannual variability. Furthermore, it is suggested that this intensification of the ENSO-monsoon relationship is likely due to the enhanced ENSO variability induced by the weakened THC. This study indicates that the low frequency fluctuation of Atlantic SSTs might have an influence on South Asian summer monsoon interannual variability and the ENSO-monsoon interaction, and suggests a nonlocal mechanism for the observed decadal-multidecadal modulation of ENSO-monsoon relationship.