Configuration interaction wave functions: A seniority number approach

This work deals with the configuration interaction method when an N-electron Hamiltonian is projected on Slater determinants which are classified according to their seniority number values. We study the spin features of the wave functions and the size of the matrices required to formulate states of any spin symmetry within this treatment. Correlation energies associated with the wave functions arising from the seniority-based configuration interaction procedure are determined for three types of molecular orbital basis: canonical molecular orbitals, natural orbitals, and the orbitals resulting from minimizing the expectation value of the N-electron seniority number operator. The performance of these bases is analyzed by means of numerical results obtained from selected N-electron systems of several spin symmetries. The comparison of the results highlights the efficiency of the molecular orbital basis which minimizes the mean value of the seniority number for a state, yielding energy values closer to those provided by the full configuration interaction procedure.Fil: Alcoba, Diego Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; ArgentinaFil: Torre, Alicia. Universidad del Pais Vasco; EspañaFil: Lain, Luis . Universidad del Pais Vasco; EspañaFil: Massaccesi, Gustavo Ernesto. Universidad de Buenos Aires. Ciclo Básico Común; ArgentinaFil: Oña, Ofelia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentin

Drawing information from the ground state G-particle-hole matrix to study electronic excited states

Very recently, we have shown the suitability to combine the G-particle-hole Hypervirial (GHV) equation method (Alcoba et al. in Int J Quantum Chem 109:3178, 2009) with the Hermitian Operator (HO) method (Bouten et al. in Nucl Phys A 202:127, 1973) for computing various energy differences of an electronic system spectrum (Valdemoro et al. in J Math Chem 50:492, 2012). The purpose of this paper is to extend our preliminary studies by applying the combined GHV-HO method to obtain the set of ground and low-lying excited states potential energy curves of several selected electronic systems. The calculations confirm the reliability of the method.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions

This work extends the concept of seniority number, which has been widely used for classifying N-electron Slater determinants, to wave functions of N electrons and spin S, as well as to N-electron spin-adapted Hilbert spaces. We propose a spin-free formulation of the seniority number operator and perform a study on the behavior of the expectation values of this operator under transformations of the molecular basis sets. This study leads to propose a quantitative evaluation for the convergence of the expansions of the wave functions in terms of Slater determinants. The non-invariant character of the seniority number operator expectation value of a wave function with respect to a unitary transformation of the molecular orbital basis set, allows us to search for a change of basis which minimizes that expectation value. The results found in the description of wave functions of selected atoms and molecules show that the expansions expressed in these bases exhibit a more rapid convergence than those formulated in the canonical molecular orbital bases and even in the natural orbital ones.Fil: Alcoba, Diego Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; ArgentinaFil: Torre, Alicia. Universidad del País Vasco. Facultad de Ciencia y Tecnología. Departamento de Química Física; España;Fil: Lain, Luis. Universidad del País Vasco. Facultad de Ciencia y Tecnología. Departamento de Química Física; España;Fil: Massaccesi, Gustavo Ernesto. Universidad de Buenos Aires. Ciclo Básico Común; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Matemática; ArgentinaFil: Oña, Ofelia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentin

Erosion consequences on beach functions along the Maresme coast (NW Mediterranean, Spain)

A methodology to analyse the influence of erosion on beach functions at a regional scale is presented. The method considers erosion hazards at different timescales and assesses consequences by evaluating impacts on recreation and protection functions. To provide useful information to decision makers for managing these functions, hazard and consequences are integrated at the municipal level within a risk matrix. This methodology is applied at the Maresme, a 45-km sandy coast situated northward of Barcelona, which supports a strong urban and infrastructure development as well as an intensive beach recreational use. Obtained results indicate differentiated erosion implications along the region, depending on the management target considered. Thus, southern municipalities are more prone to erosion affecting the protection function of the beach and leisure use by the local population, whereas erosion will have a greater effect on foreign tourism in the northern municipalities. These results highlight the necessity to employ an articulated erosion risk assessment focusing on specific targets depending on the site in question. This methodology can help coastal managers to adopt tailored measures to manage erosion impacts towards specific goals, in a more efficient and sustainable manner

Hellmann-Feynman theorem and fluctuation-correlation analysis of the Calogero-Sutherland model

Exploiting the results of the exact solution for the ground state of the one-dimensional spinless quantum gas of Fermions and impenetrable Bosons with the mu/x_{ij}^2 particle-particle interaction, the Hellmann-Feynman theorem yields mutually compensating divergences of both the kinetic and the interaction energy in the limiting case mu to -1/4. These divergences result from the peculiar behavior of both the momentum distribution (for large momenta) and the pair density (for small inter-particle separation). The available analytical pair densities for mu=-1/4, 0, and 2 allow to analyze particle-number fluctuations. They are suppressed by repulsive interaction (mu>0), enhanced by attraction (mu<0), and may therefore measure the kind and strength of correlation. Other recently proposed purely quantum-kinematical measures of the correlation strength arise from the small-separation behavior of the pair density or - for Fermions - from the non-idempotency of the momentum distribution and its large-momenta behavior. They are compared with each other and with reference-free, short-range correlation-measuring ratios of the kinetic and potential energies.Comment: 30 pages, 9 figures, revised version, short version appeared as PRB 62, 15279-15282 (2000

The Tordera Delta, a hotspot to storm impacts in the coast northwards ofBarcelona (NW Mediterranean)

The Catalan coast, as most of the developed Mediterranean coastal zone, can be characterized as a high-risk area to the impact of storms due to the large concentrationof values together with the dominance of eroding shorelines. In consequence, any long-term coastal management scheme must include a risk analysis to permitdecision makers to better allocate resources. This can be done in a nested approach in which hotspots are first identified along the coast at a regional scale andsecondly, they are further analysed to produce dedicated risk reduction strategies. In this work, we apply the methodology developed within the RISC-KIT project foridentifying and analysing coastal hotspots in the Catalan coast as a test for applying it to Mediterranean conditions. Obtained results show that this methodology isvery efficient in identifying hotspots of storm-induced flooding and erosion at a regional scale. The adoption of the response approach resulted in the direct assessmentof the hazards' probability distributions, which allowed for the selection of the severity of the hotspots to be identified. When a given coastal stretch behaves as ahotspot for both hazards, it is identified as a very highly-sensitive area to storm impacts. In the study area, the Tordera Delta possesses this condition of very high“hotspotness.” This has been demonstrated by the large and frequent damages suffered by the site during the past decades. The paper analyses different aspects related to the risk management of this area, including stakeholder actions

Erratum: Spin structure and properties of the correlation matrices corresponding to pure spin states: Controlling the s-representability of these matrices (International Journal of Quantum Chemistry (2005) 102 (629-644))

Fil: Alcoba, Diego Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; ArgentinaFil: Valdemoro, C.. Csic - Instituto de Matemáticas y Física Fundamental

Spin Adapted Reduced Hamiltonians in a Non-Orrhogonal Basis Set Representation

The formalism of spin-adepted reduced Hamiltonians has been formulated so far on the assumption that the underlying orbital space is orthonormalized. In this paper, the formalism is generalized to the non-orthogonal case, which may be important if the basis set of atomic orbitals is used or when studying intermolecular interactions