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

Variational calculation of vibrational linear and nonlinear optical properties

A variational approach for reliably calculating vibrational linear and nonlinear optical properties of molecules with large electrical and/or mechanical anharmonicity is introduced. This approach utilizes a self-consistent solution of the vibrational Schrödinger equation for the complete field-dependent potential-energy surface and, then, adds higher-level vibrational correlation corrections as desired. An initial application is made to static properties for three molecules of widely varying anharmonicity using the lowest-level vibrational correlation treatment (i.e., vibrational Møller-Plesset perturbation theory). Our results indicate when the conventional Bishop-Kirtman perturbation method can be expected to break down and when high-level vibrational correlation methods are likely to be required. Future improvements and extensions are discussed

Numerical model of solid phase transformations governed by nucleation and growth: microstructure development during isothermal crystallization

A simple numerical model which calculates the kinetics of crystallization involving randomly distributed nucleation and isotropic growth is presented. The model can be applied to different thermal histories and no restrictions are imposed on the time and the temperature dependences of the nucleation and growth rates. We also develop an algorithm which evaluates the corresponding emerging grain-size distribution. The algorithm is easy to implement and particularly flexible, making it possible to simulate several experimental conditions. Its simplicity and minimal computer requirements allow high accuracy for two- and three-dimensional growth simulations. The algorithm is applied to explore the grain morphology development during isothermal treatments for several nucleation regimes. In particular, thermal nucleation, preexisting nuclei, and the combination of both nucleation mechanisms are analyzed. For the first two cases, the universal grain-size distribution is obtained. The high accuracy of the model is stated from its comparison to analytical predictions. Finally, the validity of the Kolmogorov-Johnson-Mehl-Avrami model SSSR, is verified for all the cases studied

Desenvolupament, implementació i aplicació de noves metodologies per a l'estudi de la reactivitat química i de les propietats òptiques no lineals

El coneixement de la superfície d'energia potencial (PES) ha estat essencial en el món de la química teòrica per tal de discutir tant la reactivitat química com l'estructura i l'espectroscòpia molecular. En el camp de la reactivitat química es hem proposat continuar amb el desenvolupament de nova metodologia dins el marc de la teoria del funcional de la densitat conceptual. En particular aquesta tesis es centrarà en els següents punts: a) El nombre i la naturalesa dels seus punts estacionaris del PES poden sofrir canvis radicals modificant el nivell de càlcul utilitzats, de tal manera que per estar segurs de la seva naturalesa cal anar a nivells de càlcul molt elevats. La duresa és una mesura de la resistència d'un sistema químic a canviar la seva configuració electrònica, i segons el principi de màxima duresa on hi hagi un mínim o un màxim d'energia trobarem un màxim o un mínim de duresa, respectivament. A l'escollir tot un conjunt de reaccions problemàtiques des del punt de vista de presència de punts estacionaris erronis, hem observat que els perfils de duresa són més independents de la base i del mètode utilitzats, a més a més sempre presenten el perfil correcte. b) Hem desenvolupat noves expressions basades en les integracions dels kernels de duresa per tal de determinar la duresa global d'una molècula de manera més precisa que la utilitzada habitualment que està basada en el càlcul numèric de la derivada segona de l'energia respecte al número d'electrons. c) Hem estudiat la validesa del principis de màxima duresa i de mínima polaritzabiliat en les vibracions asimètriques en sistemes aromàtics. Hem trobat que per aquests sistemes alguns modes vibracionals incompleixen aquests principis i hem analitzat la relació d'aquest l'incompliment amb l'efecte de l'acoblament pseudo-Jahn-Teller. A més a més, hem postulat tot un conjunt de regles molt senzilles que ens permetien deduir si una molècula compliria o no aquests principis sense la realització de cap càlcul previ. Tota aquesta informació ha estat essencial per poder determinar exactament quines són les causes del compliment o l'incompliment del MHP i MPP. d) Finalment, hem realitzat una expansió de l'energia funcional en termes del nombre d'electrons i de les coordenades normals dintre del conjunt canònic. En la comparació d'aquesta expansió amb l'expansió de l'energia del nombre d'electrons i del potencial extern hem pogut recuperar d'una altra forma diferent tot un conjunt de relacions ja conegudes entre alguns coneguts descriptors de reactivitat del funcional de la densitat i en poden establir tot un conjunt de noves relacions i de nous descriptors. Dins del marc de les propietats moleculars es proposa generalitzar i millorar la metodologia pel càlcul de la contribució vibracional (Pvib) a les propietats òptiques no lineals (NLO). Tot i que la Pvib no s'ha tingut en compte en la majoria dels estudis teòrics publicats de les propietats NLO, recentment s'ha comprovat que la Pvib de diversos polímers orgànics amb altes propietats òptiques no lineals és fins i tot més gran que la contribució electrònica. Per tant, tenir en compte la Pvib és essencial en el disseny dels nous materials òptics no lineals utilitzats en el camp de la informàtica, les telecomunicacions i la tecnologia làser. Les principals línies d'aquesta tesis sobre aquest tema són: a) Hem calculat per primera vegada els termes d'alt ordre de Pvib de diversos polímers orgànics amb l'objectiu d'avaluar la seva importància i la convergència de les sèries de Taylor que defineixen aquestes contribucions vibracionals. b) Hem avaluat les contribucions electròniques i vibracionals per una sèrie de molècules orgàniques representatives utilitzant diferents metodologies, per tal de poder de determinar quina és la manera més senzilla per poder calcular les propietats NLO amb una precisió semiquantitativa.

Numerical Response of Breeding Birds Following Experimental Selection Harvesting in Northern Hardwood Forests

Silvicultural treatments have been shown to alter the composition of species assemblages in numerous taxa. However, the intensity and persistence of these effects have rarely been documented. We used a before-after, control-impact (BACI) paired design, i.e., five pairs of 25-ha study plots, 1-control and 1-treated plot, to quantify changes in the density of eight forest bird species in response to selection harvesting over six breeding seasons, one year pre- and five years postharvest. Focal species included mature forest associates, i.e., Northern Parula (Setophaga americana) and Black-throated Green Warbler (Setophaga virens), forest generalists, i.e., Yellow-bellied Sapsucker (Sphyrapicus varius) and Swainson’s Thrush (Catharus ustulatus), early-seral specialists, i.e., Mourning Warbler (Geothlypis philadelphia) and Chestnut-sided Warbler (Setophaga pensylvanica), species associated with shrubby forest gaps, i.e., Black-throated Blue Warbler (Setophaga caerulescens), and mid-seral species, i.e., American Redstart (Setophaga ruticilla). As predicted, we found a negative numerical response to the treatment in the Black-throated Green Warbler, no treatment effect in the Yellow-bellied Sapsucker, and a positive treatment effect in early-seral specialists. We only detected a year effect in the Northern Parula and the American Redstart. There was evidence for a positive treatment effect on the Swainson’s Thrush when the regeneration started to reach the pole stage, i.e., fifth year postharvest. These findings suggest that selection harvesting has the potential to maintain diverse avian assemblages while allowing sustainable management of timber supply, but future studies should determine whether mature-forest associates can sustain second- and third-entry selection harvest treatments.

On the impact of humidity observations in numerical weather prediction

The impact of humidity observations on forecast skill is explored by producing a series of global forecasts using initial data derived from the ERA-40 reanalyses system, in which all humidity data have been removed during the data assimilation. The new forecasts have been compared with the original ERA-40 analyses and forecasts made from them. Both sets of forecasts show virtually identical prediction skill in the extratropics and the tropics. Differences between the forecasts are small and undergo characteristic amplification rate. There are larger differences in temperature and geopotential in the tropics but the differences are small-scale and unstructured and have no noticeable effect on the skill of the wind forecasts. The results highlight the current very limited impact of the humidity observations, used to produce the initial state, on the forecasts.

Numerical simulation of baroclinic waves with a parameterized boundary layer

A dry three-dimensional baroclinic life cycle model is used to investigate the role of turbulent fluxes of heat and momentum within the boundary layer on mid-latitude cyclones. Simulations are performed of life cycles for two basic states, both with and without turbulent fluxes. The different basic states produce cyclones with contrasting frontal and mesoscale-flow structures. The analysis focuses on the generation of potential-vorticity (PV) in the boundary layer and its subsequent transport into the free troposphere. The dynamic mechanism through which friction mitigates a barotropic vortex is that of Ekman pumping. This has often been assumed to be also the dominant mechanism for baroclinic developments. The PV framework highlights an additional, baroclinic mechanism. Positive PV is generated baroclinically due to friction to the north-east of a surface low and is transported out of the boundary layer by a cyclonic conveyor belt flow. The result is an anomaly of increased static stability in the lower troposphere which restricts the growth of the baroclinic wave. The reduced coupling between lower and upper levels can be sufficient to change the character of the upper-level evolution of the mature wave. The basic features of the baroclinic damping mechanism are robust for different frontal structures, with and without turbulent heat fluxes, and for the range of surface roughness found over the oceans.

A cell by cell anisotropic adaptive mesh ALE scheme for the numerical solution of the Euler equations

In this paper a cell by cell anisotropic adaptive mesh technique is added to an existing staggered mesh Lagrange plus remap finite element ALE code for the solution of the Euler equations. The quadrilateral finite elements may be subdivided isotropically or anisotropically and a hierarchical data structure is employed. An efficient computational method is proposed, which only solves on the finest level of resolution that exists for each part of the domain with disjoint or hanging nodes being used at resolution transitions. The Lagrangian, equipotential mesh relaxation and advection (solution remapping) steps are generalised so that they may be applied on the dynamic mesh. It is shown that for a radial Sod problem and a two-dimensional Riemann problem the anisotropic adaptive mesh method runs over eight times faster.

Stratosphere-troposphere transport in a numerical simulation of midlatitude convection

The transport of stratospheric air deep into the troposphere via convection is investigated numerically using the UK Met Office Unified Model. A convective system that formed on 27 June 2004 near southeast England, in the vicinity an upper level potential vorticity anomaly and a lowered tropopause, provides the basis for analysis. Transport is diagnosed using a stratospheric tracer that can either be passed through or withheld from the model’s convective parameterization scheme. Three simulations are performed at increasingly finer resolutions, with horizontal grid lengths of 12, 4, and 1 km. In the 12 and 4 km simulations, tracer is transported deeply into the troposphere by the parameterized convection. In the 1 km simulation, for which the convective parameterization is disengaged, deep transport is still accomplished but with a much smaller magnitude. However, the 1 km simulation resolves stirring along the tropopause that does not exist in the coarser simulations. In all three simulations, the concentration of the deeply transported tracer is small, three orders of magnitude less than that of the shallow transport near the tropopause, most likely because of the efficient dilution of parcels in the lower troposphere.