A comparative analysis of two methods for the calculation of electric-field-induced perturbations to molecular vibration

Two common methods of accounting for electric-field-induced perturbations to molecular vibration are analyzed and compared. The first method is based on a perturbation-theoretic treatment and the second on a finite-field treatment. The relationship between the two, which is not immediately apparent, is made by developing an algebraic formalism for the latter. Some of the higher-order terms in this development are documented here for the first time. As well as considering vibrational dipole polarizabilities and hyperpolarizabilities, we also make mention of the vibrational Stark effec

A quantum molecular similarity analysis of changes in molecular electron density caused by basis set flotation and electric field application

Quantum molecular similarity (QMS) techniques are used to assess the response of the electron density of various small molecules to application of a static, uniform electric field. Likewise, QMS is used to analyze the changes in electron density generated by the process of floating a basis set. The results obtained show an interrelation between the floating process, the optimum geometry, and the presence of an external field. Cases involving the Le Chatelier principle are discussed, and an insight on the changes of bond critical point properties, self-similarity values and density differences is performed

Initial convergence of the perturbation series expansion for vibrational nonlinear optical properties

Initial convergence of the perturbation series expansion for vibrational nonlinear optical (NLO) properties was analyzed. The zero-point vibrational average (ZPVA) was obtained through first-order in mechanical plus electrical anharmonicity. Results indicated that higher-order terms in electrical and mechanical anharmonicity can make substantial contributions to the pure vibrational polarizibility of typical NLO molecules

Desenvolupament d'un sistema de previsió de risc d'infecció per Stemphylium vesicarium. Avaluació, validació i implementació en parcel·les experimentals en camps comercials de perera

L'estemfiliosi de la perera és una malaltia fúngica ocasionada pel fong Deuteromicet Stemphylium vesicarium. Els símptomes característics d'aquesta malaltia són lesions necròtiques en fulles i fruits, provocant el depreciament econòmic d'aquests últims. Si les condicions climàtiques són favorables aquesta malaltia pot arribar a provocar la pèrdua total de la producció. La malaltia es localitza bàsicament en la conca mediterrània, sent les zones fructícoles de Girona a Catalunya i Emilia-Romagna a Itàlia els llocs on les pèrdues de producció són més grans. Actualment l'únic mètode de control és la cobertura permanent dels òrgans de la planta amb fungicides. Per obtenir aquesta protecció és necessari realitzar aplicacions preventives amb una cadència fixa, setmanal o quinzenal, de diferents fungicides en els arbres. Aquesta cadència d'aplicació comporta que al llarg del període vegetatiu de la perera es realitzin entre 20 i 25 aplicacions de fungicida, per cadències setmanals, o entre 10 i 13 aplicacions si la cadència és quinzenal. Aquest elevat nombre de tractaments comporta uns efectes toxicològics a nivell mediambiental i per a la salut humana, un augment del cost econòmic de la producció i en alguns casos afavorir l'aparició de resistències del patogen a determinats fungicides. Molts d' aquests tractaments es realitzen sense que les condicions ambientals siguin favorables a l'inici d'infeccions del fong, i són per tant innecessàries. Amb l'objectiu d'obtenir una eina per determinar el risc d'infeccions en funció de les condicions climàtiques i realitzar d'aquesta manera els tractaments amb fungicides només quan són necessaris, es va elaborar el Sistema pel Tractament Racionalitzat de l'Estemfiliosi de la Perera (STREP). El model consisteix en relacionar quantitativament amb la severitat de la malaltia els paràmetres climàtics de durada del període d'humectació i temperatura mitjana durant aquests períodes. En aquest treball s'ha determinat l'eficàcia en el control de la malaltia per diferents fungicides aplicats de manera preventiva amb una cadència fixa en diferents finques comercials i durant varis anys. S'ha constatat que no hi ha cap producte totalment eficaç en el control de la malaltia, sent l'eficàcia obtinguda mitjana. Aquesta eficàcia de control esta en funció del nivell de pressió de la malaltia, obtenint eficàcies inferiors quan el nivell en els testimonis no tractats és elevat. En assajos en condicions controlades s'ha determinat que els fungicides analitzats aplicats de manera curativa o postinfecciosa, quan ja s'han iniciat les infeccions, presenten una eficàcia més baixa que quan s'apliquen preventivament. El tiram és el producte amb una eficàcia més elevada en la major part de les condicions experimentals. S' ha analitzat durant 5 anys, 1992-1996, en diferents plantacions de perera de Girona, la dinàmica dels paràmetres ambientals de durada deis períodes amb humectació, la temperatura mitjana de l'aire, la temperatura mitjana durant els períodes d'humectació, la durada dels períodes amb humitat relativa superior al 90% i la pluviometria. S 'ha constatat que la humectació deguda a la rosada és la principal causa d'humectació i que és un procés lent i continu. Les durades més freqüents d'humectació han estat períodes inferiors a 12 hores i les temperatures més freqüents durant aquests períodes han estat entre 11 i 21°C. S'ha determinat també que existeixen períodes amb humitat relativa elevada però sense formació de pel·lícula d'aigua i s'ha observat que ocasionalment existeixen períodes breus d'interrupció de la humectació en que poden existir humanitats relatives elevades o baixes. La capacitat predictiva del model STREP ha estat avaluada mitjançant 42 assajos en condicions naturals i controlades, determinant que en més del 95 % dels casos avaluats les prediccions de malaltia s'han correspost amb les observades, i que només en dos casos el model ha infraestimat el nivell de risc d'infecció. Demostrant així que el model STREP és fiable en les seves prediccions. S'ha estudiat l'efecte de la humitat relativa durant els períodes interromputs d'humectació i les durades d'aquests períodes, en les infeccions produïdes pel fong. S'ha constatat que el model STREP hauria d'incorporar com a períodes separats els períodes d'humectació interromputs amb relatives elevades (>98%) s'haurien de considerar com a períodes continus. Per una altra banda s'ha comprovat que els períodes amb humitats relatives elevades sense formació d'humectació en condicions naturals no són suficients per provocar l'inici d'infeccions de S. Vesicarium. S'ha utilitzat el model STREP com a eina per guiar els tractaments fungicides en diferents parcel·les de finques comercials durant dos anys. D'aquests assajos es pot concloure que utilitzant valors de risc acumulat SA:0.4 com a llindar per a realitzar els tractaments es controla la malaltia amb una eficàcia semblant als tractaments setmanals, però amb una reducció del nombre d'aplicacions necessàries entre un 25 i un 50%. Utilitzar un llindar SA:0.6 en finques amb varietats sensibles i una pressió d'inòcul del patogen elevada presenta bons resultats però inferiors als obtinguts amb tractaments setmanals, no obstant l'estalvi de tractaments ha estat molt important (50-70%). De tots aquests resultats es conclou que el model STREP és adequat per ésser utilitzat en programes pilot a escala comercial en el control racional de l'estemfiliosi de la perera. En funció d'aquests resultats es considerarà la seva implementació en Estacions d'Avisos Fitosanitaris.

Theoretical studies of systems of biochemical interest containing Fe and Cu transition metals

La presència de la química teòrica i computacional està augmentant en quasi tots els camps de la recerca en química. Els càlculs teòrics poden ajudar a entendre millor l'estructura, les propietats i la reactivitat de compostos metàl·lics d'àrees tan diferents com la química inorgànica, organometàl·lica i bioinorgànica. No obstant això, és imprescindible utilitzar la metodologia adequada per obtenir resultats teòrics fiables. Els estudis d'aquesta tesi es poden dividir en dos grups diferents. El primer grup inclou l'estudi teòric del mecanisme de reacció de diversos sistemes que contenen coure i tenen diferents estructures Cun-O2. Aquests estudies s'han dut a terme amb l'objectiu de profunditzar en la natura dels processos oxidants químics i biològics promoguts per sistemes que contenen coure. En la segona part de la tesi, s'estudia la fiabilitat de diferents tècniques utilitzades per estudiar l'estructura electrònica i la reactivitat de sistemes que contenen coure, ferro i altres metalls de transició.

Case based reasoning as an extension of fault dictionary methods for linear electronic analog circuits diagnosis

El test de circuits és una fase del procés de producció que cada vegada pren més importància quan es desenvolupa un nou producte. Les tècniques de test i diagnosi per a circuits digitals han estat desenvolupades i automatitzades amb èxit, mentre que aquest no és encara el cas dels circuits analògics. D'entre tots els mètodes proposats per diagnosticar circuits analògics els més utilitzats són els diccionaris de falles. En aquesta tesi se'n descriuen alguns, tot analitzant-ne els seus avantatges i inconvenients. Durant aquests últims anys, les tècniques d'Intel·ligència Artificial han esdevingut un dels camps de recerca més importants per a la diagnosi de falles. Aquesta tesi desenvolupa dues d'aquestes tècniques per tal de cobrir algunes de les mancances que presenten els diccionaris de falles. La primera proposta es basa en construir un sistema fuzzy com a eina per identificar. Els resultats obtinguts son força bons, ja que s'aconsegueix localitzar la falla en un elevat tant percent dels casos. Per altra banda, el percentatge d'encerts no és prou bo quan a més a més s'intenta esbrinar la desviació. Com que els diccionaris de falles es poden veure com una aproximació simplificada al Raonament Basat en Casos (CBR), la segona proposta fa una extensió dels diccionaris de falles cap a un sistema CBR. El propòsit no és donar una solució general del problema sinó contribuir amb una nova metodologia. Aquesta consisteix en millorar la diagnosis dels diccionaris de falles mitjançant l'addició i l'adaptació dels nous casos per tal d'esdevenir un sistema de Raonament Basat en Casos. Es descriu l'estructura de la base de casos així com les tasques d'extracció, de reutilització, de revisió i de retenció, fent èmfasi al procés d'aprenentatge. En el transcurs del text s'utilitzen diversos circuits per mostrar exemples dels mètodes de test descrits, però en particular el filtre biquadràtic és l'utilitzat per provar les metodologies plantejades, ja que és un dels benchmarks proposats en el context dels circuits analògics. Les falles considerades son paramètriques, permanents, independents i simples, encara que la metodologia pot ser fàcilment extrapolable per a la diagnosi de falles múltiples i catastròfiques. El mètode es centra en el test dels components passius, encara que també es podria extendre per a falles en els actius.

Les ceràmiques de producció ibèrica de Sant Julià de Ramis: el poblat i els camps de sitges

The paper analyzes the Iberian ceramics from Sant Julià de Ramis (Girona). The scope of research includes the village itself and other archaeological sites as areas of the Bosc del Congosts silos and Escalers. The research draws several archaeological material dug up in the Iberian site and made in the fields of silos.

Detection of flood extent in urban areas using high resolution TerraSAR-X data

Flooding is a major hazard in both rural and urban areas worldwide, but it is in urban areas that the impacts are most severe. An investigation of the ability of high resolution TerraSAR-X data to detect flooded regions in urban areas is described. An important application for this would be the calibration and validation of the flood extent predicted by an urban flood inundation model. To date, research on such models has been hampered by lack of suitable distributed validation data. The study uses a 3m resolution TerraSAR-X image of a 1-in-150 year flood near Tewkesbury, UK, in 2007, for which contemporaneous aerial photography exists for validation. The DLR SETES SAR simulator was used in conjunction with airborne LiDAR data to estimate regions of the TerraSAR-X image in which water would not be visible due to radar shadow or layover caused by buildings and taller vegetation, and these regions were masked out in the flood detection process. A semi-automatic algorithm for the detection of floodwater was developed, based on a hybrid approach. Flooding in rural areas adjacent to the urban areas was detected using an active contour model (snake) region-growing algorithm seeded using the un-flooded river channel network, which was applied to the TerraSAR-X image fused with the LiDAR DTM to ensure the smooth variation of heights along the reach. A simpler region-growing approach was used in the urban areas, which was initialized using knowledge of the flood waterline in the rural areas. Seed pixels having low backscatter were identified in the urban areas using supervised classification based on training areas for water taken from the rural flood, and non-water taken from the higher urban areas. Seed pixels were required to have heights less than a spatially-varying height threshold determined from nearby rural waterline heights. Seed pixels were clustered into urban flood regions based on their close proximity, rather than requiring that all pixels in the region should have low backscatter. This approach was taken because it appeared that urban water backscatter values were corrupted in some pixels, perhaps due to contributions from side-lobes of strong reflectors nearby. The TerraSAR-X urban flood extent was validated using the flood extent visible in the aerial photos. It turned out that 76% of the urban water pixels visible to TerraSAR-X were correctly detected, with an associated false positive rate of 25%. If all urban water pixels were considered, including those in shadow and layover regions, these figures fell to 58% and 19% respectively. These findings indicate that TerraSAR-X is capable of providing useful data for the calibration and validation of urban flood inundation models.

Extraction of tidal channel networks from aerial photographs alone and combined with laser altimetry

Tidal channel networks play an important role in the intertidal zone, exerting substantial control over the hydrodynamics and sediment transport of the region and hence over the evolution of the salt marshes and tidal flats. The study of the morphodynamics of tidal channels is currently an active area of research, and a number of theories have been proposed which require for their validation measurement of channels over extensive areas. Remotely sensed data provide a suitable means for such channel mapping. The paper describes a technique that may be adapted to extract tidal channels from either aerial photographs or LiDAR data separately, or from both types of data used together in a fusion approach. Application of the technique to channel extraction from LiDAR data has been described previously. However, aerial photographs of intertidal zones are much more commonly available than LiDAR data, and most LiDAR flights now involve acquisition of multispectral images to complement the LiDAR data. In view of this, the paper investigates the use of multispectral data for semiautomatic identification of tidal channels, firstly from only aerial photographs or linescanner data, and secondly from fused linescanner and LiDAR data sets. A multi-level, knowledge-based approach is employed. The algorithm based on aerial photography can achieve a useful channel extraction, though may fail to detect some of the smaller channels, partly because the spectral response of parts of the non-channel areas may be similar to that of the channels. The algorithm for channel extraction from fused LiDAR and spectral data gives an increased accuracy, though only slightly higher than that obtained using LiDAR data alone. The results illustrate the difficulty of developing a fully automated method, and justify the semi-automatic approach adopted.

Remote sensing of tidal networks and their relation to vegetation

The study of the morphology of tidal networks and their relation to salt marsh vegetation is currently an active area of research, and a number of theories have been developed which require validation using extensive observations. Conventional methods of measuring networks and associated vegetation can be cumbersome and subjective. Recent advances in remote sensing techniques mean that these can now often reduce measurement effort whilst at the same time increasing measurement scale. The status of remote sensing of tidal networks and their relation to vegetation is reviewed. The measurement of network planforms and their associated variables is possible to sufficient resolution using digital aerial photography and airborne scanning laser altimetry (LiDAR), with LiDAR also being able to measure channel depths. A multi-level knowledge-based technique is described to extract networks from LiDAR in a semi-automated fashion. This allows objective and detailed geomorphological information on networks to be obtained over large areas of the inter-tidal zone. It is illustrated using LIDAR data of the River Ems, Germany, the Venice lagoon, and Carnforth Marsh, Morecambe Bay, UK. Examples of geomorphological variables of networks extracted from LiDAR data are given. Associated marsh vegetation can be classified into its component species using airborne hyperspectral and satellite multispectral data. Other potential applications of remote sensing for network studies include determining spatial relationships between networks and vegetation, measuring marsh platform vegetation roughness, in-channel velocities and sediment processes, studying salt pans, and for marsh restoration schemes.

LiDAR mapping of tidal marshes for ecogeomorphological modelling in the TIDE project

The European research project TIDE (Tidal Inlets Dynamics and Environment) is developing and validating coupled models describing the morphological, biological and ecological evolution of tidal environments. The interactions between the physical and biological processes occurring in these regions requires that the system be studied as a whole rather than as separate parts. Extensive use of remote sensing including LiDAR is being made to provide validation data for the modelling. This paper describes the different uses of LiDAR within the project and their relevance to the TIDE science objectives. LiDAR data have been acquired from three different environments, the Venice Lagoon in Italy, Morecambe Bay in England, and the Eden estuary in Scotland. LiDAR accuracy at each site has been evaluated using ground reference data acquired with differential GPS. A semi-automatic technique has been developed to extract tidal channel networks from LiDAR data either used alone or fused with aerial photography. While the resulting networks may require some correction, the procedure does allow network extraction over large areas using objective criteria and reduces fieldwork requirements. The networks extracted may subsequently be used in geomorphological analyses, for example to describe the drainage patterns induced by networks and to examine the rate of change of networks. Estimation of the heights of the low and sparse vegetation on marshes is being investigated by analysis of the statistical distribution of the measured LiDAR heights. Species having different mean heights may be separated using the first-order moments of the height distribution.

Computer modelling and estimation of recruitment patterns of non-branching coral colonies at three sites in Wakatobi Marine Park, S.E. Sulawesi, Indonesia; implications for coral reef conservation

We have studied growth and estimated recruitment of massive coral colonies at three sites, Kaledupa, Hoga and Sampela, separated by about 1.5 km in the Wakatobi Marine National Park, S.E. Sulawesi, Indonesia. There was significantly higher species richness (P<0.05), coral cover (P<0.05) and rugosity (P<0.01) at Kaledupa than at Sampela. A model for coral reef growth has been developed based on a rational polynomial function, where dx/dt is an index of coral growth with time; W is the variable (for example, coral weight, coral length or coral area), up to the power of n in the numerator and m in the denominator; a1……an and b1…bm are constants. The values for n and m represent the degree of the polynomial, and can relate to the morphology of the coral. The model was used to simulate typical coral growth curves, and tested using published data obtained by weighing coral colonies underwater in reefs on the south-west coast of Curaçao [‘Neth. J. Sea Res. 10 (1976) 285’]. The model proved an accurate fit to the data, and parameters were obtained for a number of coral species. Surface area data was obtained on over 1200 massive corals at three different sites in the Wakatobi Marine National Park, S.E. Sulawesi, Indonesia. The year of an individual's recruitment was calculated from knowledge of the growth rate modified by application of the rational polynomial model. The estimated pattern of recruitment was variable, with little numbers of massive corals settling and growing before 1950 at the heavily used site, Sampela, relative to the reef site with little or no human use, Kaledupa, and the intermediate site, Hoga. There was a significantly greater sedimentation rate at Sampela than at either Kaledupa (P<0.0001) or Hoga (P<0.0005). The relative mean abundance of fish families present at the reef crests at the three sites, determined using digital video photography, did not correlate with sedimentation rates, underwater visibility or lack of large non-branching coral colonies. Radial growth rates of three genera of non-branching corals were significantly lower at Sampela than at Kaledupa or at Hoga, and there was a high correlation (r=0.89) between radial growth rates and underwater visibility. Porites spp. was the most abundant coral over all the sites and at all depths followed by Favites (P<0.04) and Favia spp. (P<0.03). Colony ages of Porites corals were significantly lower at the 5 m reef flat on the Sampela reef than at the same depth on both other reefs (P<0.005). At Sampela, only 2.8% of corals on the 5 m reef crest are of a size to have survived from before 1950. The Scleractinian coral community of Sampela is severely impacted by depositing sediments which can lead to the suffocation of corals, whilst also decreasing light penetration resulting in decreased growth and calcification rates. The net loss of material from Sampela, if not checked, could result in the loss of this protective barrier which would be to the detriment of the sublittoral sand flats and hence the Sampela village.

A method of synthesis of silicious inorganic ordered materials (MCM-41-SBA-1) employing polyacrylic acid-C(n)TAB-TEOS nanoassemblies

In this work we describe the synthesis of a variety of MCM-41 type hexagonal and SBA-1 type cubic mesostructures and mesoporous silicious materials employing a novel synthesis concept based on polyacrylic acid (Pac)-C(n)TAB complexes as backbones of the developing structures. The ordered porosity of the solids was established by XRD and TEM techniques. The synthesis concept makes use of Pac-C(n)TAB nanoassemblies as a preformed scaffold, formed by the gradual increase of pH. On this starting matrix the inorganic precursor species SiO2 precipitate via hydrolysis of TEOS under the influence of increasing pH. The molecular weight (MW) of Pac, as well as the length of carbon chain in C,TAB, determine the physical and structural characteristics of the obtained materials. Longer chain surfactants (C(16)TAB) lead to the formation of hexagonal phase, while shorter chain surfactants (C(14)TAB, C(12)TAB) favor the SBA-1 phase. Lower MW of Pac (approximate to2000) leads to better-organized structures compared to higher MW ( 450,000), which leads to worm-like mesostructures. Cell parameters and pore size increase with increasing polyelectrolyte and/or surfactant chain, while at the same time SEM photography reveals that the particle size decreases. Conductivity experiments provide some insight into the proposed self-assembling pathway. (C) 2003 Elsevier Inc. All rights reserved.

Preliminary results on the non-thermal effects of 200-350 GHz radiation on the growth rate of S. cerevisiae cells in microcolonies

We report preliminary results from studies of biological effects induced by non-thermal levels of non-ionizing electromagnetic radiation. Exponentially growing Saccharomyces cerevisiae yeast cells grown on dry media were exposed to electromagnetic fields in the 200–350 GHz frequency range at low power density to observe possible non-thermal effects on the microcolony growth. Exposure to the electromagnetic field was conducted over 2.5 h. The data from exposure and control experiments were grouped into either large-, medium- or small-sized microcolonies to assist in the accurate assessment of growth. The three groups showed significant differences in growth between exposed and control microcolonies. A statistically significant enhanced growth rate was observed at 341 GHz. Growth rate was assessed every 30 min via time-lapse photography. Possible interaction mechanisms are discussed, taking into account Frohlich's hypothesis.