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

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

Impact of childhood and adulthood psychological health on labour force participation and exit in later life

Adulthood psychological health predicts labour force activity but few studies have examined childhood psychological health. We hypothesized that childhood psychological ill-health would be associated with labour force exit at 55 years. Data were from the 55-year follow-up of the National Child Development Study (n = 9137). Labour force participation and exit (unemployment, retirement, permanent sickness, homemaking/other) were self-reported at 55 years. Internalizing and externalizing problems in childhood (7, 11 and 16 years) and malaise in adulthood (23, 33, 42, 50 years) were assessed. Education, social class, periods of unemployment, partnership separations, number of children, and homemaking activity were measured throughout adulthood. Childhood internalizing and externalizing problems were associated with unemployment, permanent sickness and homemaking/other at 55 years, after adjustment for adulthood psychological health and education: one or two reports of internalizing was associated with increased risk for unemployment [relative risk (RR) 1.59, 95% confidence interval (CI) 1.12–2.25; RR 2.37, 95% CI 1.48–3.79] and permanent sickness (RR 1.32, 95% CI 1.00–1.74; RR, 1.48, 95% CI 1.00–2.17); three reports of externalizing was associated with increased risk for unemployment (RR 2.26, 95% CI 1.01–5.04), permanent sickness (RR 2.63, 95% CI 1.46–4.73) and homemaking/other (RR 1.95, 95% CI 1.00–3.78). Psychological ill-health across the lifecourse, including during childhood, reduces the likelihood of working in older age. Support for those with mental health problems at different life stages and for those with limited connections to the labour market, including homemakers, is an essential dimension of attempts to extend working lives

Variational reduced density matrix method in the doubly occupied configuration interaction space using three-particle N-representability conditions

Ground-state energies and two-particle reduced density matrices (2-RDMs) corresponding to N-particle systems are computed variationally within the doubly occupied configuration interaction (DOCI) space by constraining the 2-RDM to satisfy a complete set of three-particle N-representability conditions known as three-positivity conditions. These conditions are derived and implemented in the variational calculation of the 2-RDM with standard semidefinite programming algorithms. Ground state energies and 2-RDMs are computed for N2, CO, CN-, and NO+ molecules at both equilibrium and nonequilibrium geometries as well as for pairing models at different repulsive interaction strengths. The results from the full three-positivity conditions are compared with those from the exact DOCI method and with approximated 2-RDM variational ones obtained within two-positivity and two-positivity plus a subset of three-positivity conditions, as recently reported [D. R. Alcoba et al., J. Chem. Phys. 148, 024105 (2018) and A. Rubio-García et al., J. Chem. Theory Comput. 14, 4183 (2018)]. The accuracy of these numerical determinations and their low computational cost demonstrate the usefulness of the three-particle variational constraints within the DOCI framework.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: Capuzzi, Pablo. 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: Rubio García, Alvaro. Consejo Superior de Investigaciones Científicas; EspañaFil: Dukelsky, Jorge. Consejo Superior de Investigaciones Científicas; EspañaFil: Massaccesi, Gustavo Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Ciclo Básico Común; ArgentinaFil: Oña, Ofelia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Torre, Alicia. Universidad del País Vasco; EspañaFil: Lain, Luis. Universidad del País Vasco; Españ

Synthesis of layered silicon-graphene hetero-structures by wet jet milling for high capacity anodes in Li-ion batteries

While silicon-based negative electrode materials have been extensively studied, to develop high capacity lithium-ion batteries (LIBs), implementing a large-scale production method that can be easily transferred to industry, has been a crucial challenge. Here, a scalable wet-jet milling method was developed to prepare a silicon-graphene hybrid material to be used as negative electrode in LIBs. This synthesized composite, when used as an anode in lithium cells, demonstrated high Li ion storage capacity, long cycling stability and high-rate capability. In particular, the electrode exhibited a reversible discharge capacity exceeding 1763 mAh g−1 after 450 cycles with a capacity retention of 98% and a coulombic efficiency of 99.85% (with a current density of 358 mA g−1). This significantly supersedes the performance of a Si-dominant electrode structures. The capacity fade rate after 450 cycles was only 0.005% per cycle in the 0.05–1 V range. This superior electrochemical performance is ascribed to the highly layered, silicon-graphene porous structure, as investigated via focused ion beam in conjunction with scanning electron microscopy tomography. The hybrid electrode could retain 89% of its porosity (under a current density of 358 mA g−1) after 200 cycles compared with only 35% in a Si-dominant electrode. Moreover, this morphology can not only accommodate the large volume strains from active silicon particles, but also maintains robust electrical connectivity. This confers faster transportation of electrons and ions with significant permeation of electrolyte within the electrode. Physicochemical characterisations were performed to further correlate the electrochemical performance with the microstructural dynamics. The excellent performance of the hybrid material along with the scalability of the synthesizing process is a step forward to realize high capacity/energy density LIBs for multiple device applications

Variational determination of the two-electron reduced density matrix within the doubly occupied configuration interaction scheme: An extension to the study of open-shell systems

This work proposes to describe open-shell molecules or radicals using the framework of the doubly occupied configuration interaction (DOCI) treatments, so far limited to closed-shell system studies. The proposal is based on considering molecular systems in singlet states generated by adding extra hydrogen atoms located at infinite distance from the target radical system. The energy of this radical is obtained by subtracting the energies of the dissociated hydrogen atoms from that provided by the two-electron reduced density matrix corresponding to the singlet state system in the DOCI space, which is variationally calculated by imposing a set of N-representability conditions. This method is numerically assessed by describing potential energy curves and reduced density matrices in selected ionic and neutral open-shell systems in the doublet spin symmetry ground state.Fil: Oña, Ofelia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Torre, Alicia. Universidad del País Vasco; EspañaFil: Lain, Luis. Universidad del País Vasco; EspañaFil: 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: Ríos, Elías Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Massaccesi, Gustavo Ernesto. Universidad de Buenos Aires; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

The future of Cybersecurity in Italy: Strategic focus area

This volume has been created as a continuation of the previous one, with the aim of outlining a set of focus areas and actions that the Italian Nation research community considers essential. The book touches many aspects of cyber security, ranging from the definition of the infrastructure and controls needed to organize cyberdefence to the actions and technologies to be developed to be better protected, from the identification of the main technologies to be defended to the proposal of a set of horizontal actions for training, awareness raising, and risk management

Regional block versus general anaesthesia for caesarean section and neonatal outcomes: a population-based study

<p>Abstract</p> <p>Background</p> <p>Anaesthesia guidelines recommend regional anaesthesia for most caesarean sections due to the risk of failed intubation and aspiration with general anaesthesia. However, general anaesthesia is considered to be safe for the foetus, based on limited evidence, and is still used for caesarean sections.</p> <p>Methods</p> <p>Cohorts of caesarean sections by indication (that is, planned repeat caesarean section, failure to progress, foetal distress) were selected from the period 1998 to 2004 (<it>N </it>= 50,806). Deliveries performed under general anaesthesia were compared with those performed under spinal or epidural, for the outcomes of neonatal intubation and 5-minute Apgar (Apgar5) <7.</p> <p>Results</p> <p>The risk of adverse outcomes was increased for caesarean sections under general anaesthesia for all three indications and across all levels of hospital. The relative risks were largest for low-risk planned repeat caesarean deliveries: resuscitation with intubation relative risk was 12.8 (95% confidence interval 7.6, 21.7), and Apgar5 <7 relative risk was 13.4 (95% confidence interval 9.2, 19.4). The largest absolute increase in risk was for unplanned caesareans due to foetal distress: there were five extra intubations per 100 deliveries and six extra Apgar5 <7 per 100 deliveries.</p> <p>Conclusion</p> <p>The infants most affected by general anaesthesia were those already compromised <it>in utero</it>, as evidenced by foetal distress. The increased rate of adverse neonatal outcomes should be weighed up when general anaesthesia is under consideration.</p

A prevalence survey of every-day activities in pregnancy

<p>Abstract</p> <p>Background</p> <p>Research into the effects of common activities during pregnancy is sparse and often contradictory. To examine whether common activities are an acute trigger of pregnancy complications the prevalence of these activities are necessary to determine sample size estimates. The aim of this study is to ascertain the prevalence of selected activities in any seven day period during pregnancy.</p> <p>Methods</p> <p>The study was conducted in the antenatal clinic of a teaching hospital with tertiary obstetric and neonatal care in Sydney, Australia between August 2008 and April 2009. Women who were at least 20 weeks pregnant and able to read English completed a questionnaire to assess whether they had performed a list of activities in the seven days prior to survey completion. Results were analysed using frequency tabulations, contingency table analyses and chi square tests.</p> <p>Results</p> <p>A total of 766 surveys were completed, 29 surveys were excluded as the women completing them were less than 20 weeks pregnant, while 161 women completed the survey more than once. Ninety seven per cent of women completed the survey when approached for the first time, while 87% completed the survey when approached a subsequent time. In the week prior to completing the survey 82.6% of women had consumed a caffeinated beverage, 42.1% had had sexual intercourse, 32.7% had lifted something over 12 kilograms, 21.4% had consumed alcohol and 6.4% had performed vigorous exercise. The weekly prevalence of heavy lifting was higher for multiparous women compared to nulliparous women.</p> <p>Conclusions</p> <p>The results of this study can be used to inform future research into activities as acute triggers of pregnancy complications.</p