Application of discriminant function analysis and change-point problem in dating volcanic ashes

The application of Discriminant function analysis (DFA) is not a new idea in the study of tephrochrology. In this paper, DFA is applied to compositional datasets of two different types of tephras from Mountain Ruapehu in New Zealand and Mountain Rainier in USA. The canonical variables from the analysis are further investigated with a statistical methodology of change-point problems in order to gain a better understanding of the change in compositional pattern over time. Finally, a special case of segmented regression has been proposed to model both the time of change and the change in pattern. This model can be used to estimate the age for the unknown tephras using Bayesian statistical calibration

An alternative method for dating unknown tephras based on a segmented regression model

In CoDaWork’05, we presented an application of discriminant function analysis (DFA) to 4 different compositional datasets and modelled the first canonical variable using a segmented regression model solely based on an observation about the scatter plots. In this paper, multiple linear regressions are applied to different datasets to confirm the validity of our proposed model. In addition to dating the unknown tephras by calibration as discussed previously, another method of mapping the unknown tephras into samples of the reference set or missing samples in between consecutive reference samples is proposed. The application of these methodologies is demonstrated with both simulated and real datasets. This new proposed methodology provides an alternative, more acceptable approach for geologists as their focus is on mapping the unknown tephra with relevant eruptive events rather than estimating the age of unknown tephra. Kew words: Tephrochronology; Segmented regression

Using self organizing maps on compositional data

Self-organizing maps (Kohonen 1997) is a type of artificial neural network developed to explore patterns in high-dimensional multivariate data. The conventional version of the algorithm involves the use of Euclidean metric in the process of adaptation of the model vectors, thus rendering in theory a whole methodology incompatible with non-Euclidean geometries. In this contribution we explore the two main aspects of the problem: 1. Whether the conventional approach using Euclidean metric can shed valid results with compositional data. 2. If a modification of the conventional approach replacing vectorial sum and scalar multiplication by the canonical operators in the simplex (i.e. perturbation and powering) can converge to an adequate solution. Preliminary tests showed that both methodologies can be used on compositional data. However, the modified version of the algorithm performs poorer than the conventional version, in particular, when the data is pathological. Moreover, the conventional ap- proach converges faster to a solution, when data is \well-behaved". Key words: Self Organizing Map; Artificial Neural networks; Compositional data

Relations among several nuclear and electronic density functional reactivity indexes

A set of connections among several nuclear and electronic indexes of reactivity in the framework of the conceptual Density Functional Theory by using an expansion ofthe energy functional in terms of the total number of electrons and the normal coordinates within a canonical ensemble was derived. The relations obtained provided explicit links between important quantities related to the chemical reactivity of a system. This paper particularly demonstrates that the derivative of the electronic energy with respect to the external potential of a system in its equilibrium geometry was equal to the negative of the nuclear repulsion derivative with respect to the external potential

Estimates of electronic coupling for excess electron transfer in DNA

Electronic coupling Vda is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of Vda for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a π stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of Vda are obtained with the standard 6-31 G* and extended 6-31++ G* basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of Vda are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements Vda for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack

La catedral i Girona: l' entrada del complex episcopal dins murs entre els segles X-XI

Fins a la darreria del segle VIII, el complex episcopal gironí se situava fora murs, al voltant de l'església martirial de Sant Feliu; a principis del segle IX, el complex es desdoblà amb la consagració d'una segona església episcopal, Santa Maria, dins murs, raó per la qual la seu fou coneguda, al llarg d'aquella centúria, amb la doble advocació de Santa Maria i Sant Feliu. Al llarg del segle X, s'afermà la preeminència de Santa Maria fins al punt que, en l'últim terç del segle. Sant Feliu ja no és esmentada com a seu episcopal, encara que hi continuà vinculada com a una església dependent, sense personalitat ni administració pròpia. Des de final del segle, el procés s'accelerà amb la construcció d'una nova església catedral a Santa Maria, que complementà l'aixecament d'un nou complex episcopal dins murs, en gran part culminat a mitjan segle XI i format per xenodoquium, catedral, palau episcopal i conjunt canonical, a banda de noves residències de canonges i altres clergues en el seu entorn. Aquests fets significaren la consolidació de Santa Maria com a seu única, però també la profunda remodelació urbanística d'un sector significatiu de la ciutat, prop d'un 20% del total, expressió del nou domini del bisbe i dels clergues sobre la 'seva ciutat'