Basis set superposition error-counterpoise corrected potential energy surfaces : application to hydrogen peroxide ... X (X=F-, Cl-, Br-, Li+, Na+) complexes

Møller-Plesset (MP2) and Becke-3-Lee-Yang-Parr (B3LYP) calculations have been used to compare the geometrical parameters, hydrogen-bonding properties, vibrational frequencies and relative energies for several X- and X+ hydrogen peroxide complexes. The geometries and interaction energies were corrected for the basis set superposition error (BSSE) in all the complexes (1-5), using the full counterpoise method, yielding small BSSE values for the 6-311 + G(3df,2p) basis set used. The interaction energies calculated ranged from medium to strong hydrogen-bonding systems (1-3) and strong electrostatic interactions (4 and 5). The molecular interactions have been characterized using the atoms in molecules theory (AIM), and by the analysis of the vibrational frequencies. The minima on the BSSE-counterpoise corrected potential-energy surface (PES) have been determined as described by S. Simón, M. Duran, and J. J. Dannenberg, and the results were compared with the uncorrected PES

Determination of the direct band-gap energy of InAlAs matched to InP by photoluminescence excitation spectroscopy

A series of InxAl1-xAs samples (0.51≪x≪0.55)coherently grown on InP was studied in order to measure the band-gap energy of the lattice matched composition. As the substrate is opaque to the relevant photon energies, a method is developed to calculate the optical absorption coefficient from the photoluminescence excitation spectra. The effect of strain on the band-gap energy has been taken into account. For x=0.532, at 14 K we have obtained Eg0=1549±6 meV

The effect of counterpoise correction and relaxation energy term to the internal rotation barriers: application to the BF3 ...NH3 and C2H4 ...SO2 dimers

The relevance of the fragment relaxation energy term and the effect of the basis set superposition error on the geometry of the BF3⋯NH3 and C2H4⋯SO2 van der Waals dimers have been analyzed. Second-order Møller-Plesset perturbation theory calculations with the d95(d,p) basis set have been used to calculate the counterpoise-corrected barrier height for the internal rotations. These barriers have been obtained by relocating the stationary points on the counterpoise-corrected potential energy surface of the processes involved. The fragment relaxation energy can have a large influence on both the intermolecular parameters and barrier height. The counterpoise correction has proved to be important for these systems

A chemical Hamiltonian approach study of the basis set superposition error changes on electron densities and one- and two-center energy components

A comparision of the local effects of the basis set superposition error (BSSE) on the electron densities and energy components of three representative H-bonded complexes was carried out. The electron densities were obtained with Hartee-Fock and density functional theory versions of the chemical Hamiltonian approach (CHA) methodology. It was shown that the effects of the BSSE were common for all complexes studied. The electron density difference maps and the chemical energy component analysis (CECA) analysis confirmed that the local effects of the BSSE were different when diffuse functions were present in the calculations

Energy partitioning for "fuzzy" atoms

The total energy of molecule in terms of 'fuzzy atoms' presented as sum of one- and two-atomic energy components is described. The divisions of three-dimensional physical space into atomic regions exhibit continuous transition from one to another. The energy components are on chemical energy scale according to proper definitions. The Becke's integration scheme and weight function determines realization of method which permits effective numerical integrations

C-H···O H-bonded complexes: how does basis set superposition error change their potential-energy surfaces?

Geometries, vibrational frequencies, and interaction energies of the CNH⋯O3 and HCCH⋯O3 complexes are calculated in a counterpoise-corrected (CP-corrected) potential-energy surface (PES) that corrects for the basis set superposition error (BSSE). Ab initio calculations are performed at the Hartree-Fock (HF) and second-order Møller-Plesset (MP2) levels, using the 6-31G(d,p) and D95++(d,p) basis sets. Interaction energies are presented including corrections for zero-point vibrational energy (ZPVE) and thermal correction to enthalpy at 298 K. The CP-corrected and conventional PES are compared; the unconnected PES obtained using the larger basis set including diffuse functions exhibits a double well shape, whereas use of the 6-31G(d,p) basis set leads to a flat single-well profile. The CP-corrected PES has always a multiple-well shape. In particular, it is shown that the CP-corrected PES using the smaller basis set is qualitatively analogous to that obtained with the larger basis sets, so the CP method becomes useful to correctly describe large systems, where the use of small basis sets may be necessary

The hardness profile as a tool to detect spurious stationary points in the potential energy surface

The energy and hardness profile for a series of inter and intramolecular conformational changes at several levels of calculation were computed. The hardness profiles were found to be calculated as the difference between the vertical ionization potential and electron affinity. The hardness profile shows the correct number of stationary points independently of the basis set and methodology used. It was found that the hardness profiles can be used to check the reliability of the energy profiles for those chemical system

One- and two-center physical space partitioning of the energy in the density functional theory

A conceptually new approach is introduced for the decomposition of the molecular energy calculated at the density functional theory level of theory into sum of one- and two-atomic energy components, and is realized in the "fuzzy atoms" framework. (Fuzzy atoms mean that the three-dimensional physical space is divided into atomic regions having no sharp boundaries but exhibiting a continuous transition from one to another.) The new scheme uses the new concept of "bond order density" to calculate the diatomic exchange energy components and gives them unexpectedly close to the values calculated by the exact (Hartree-Fock) exchange for the same Kohn-Sham orbitals

Modern energy consumption and economic modernisation in Latin America and the Caribbean between 1890 and 1925

In the absence of comparable macroeconomic indicators for most of the Latin Americaneconomies before the 1930s, the apparent consumption of energy is used in this paper as a proxyof the degree of modernisation of Latin America and the Caribbean. This paper presents anestimate of the apparent consumption per head of modern energies (coal, petroleum andhydroelectricity) for 30 countries of Latin American and the Caribbean for 1890 to 1925,multiplying the number of countries for which energy consumption estimates were previouslyavailable. As a result, the paper provides the basis for a quantitative comparative analysis ofmodernisation performance beyond the few countries for which historical national accounts areavailable in Latin America.

Energy as an indicator of modernisation in Latin America by 1925

In absence of comparable macroeconomic indicators for most of the Latin American economiesbeyond the 1930s, this paper presents an estimate of the apparent consumption per head of coal and petroleum for 25 countries of Latin American and the Caribbean for the year 1925, doubling the number of countries for which energy consumption estimates were previously available. Energy consumption is then used as an indicator of economic modernisation. As a result, the paper provides the basis for a quantitative comparative analysis of modernisation performance beyond the few countries for which historical national accounts are available in Latin America.

Systematic study of the static electrical properties of the CO molecule: influence of the basis set size and correlation energy

The influence of the basis set size and the correlation energy in the static electrical properties of the CO molecule is assessed. In particular, we have studied both the nuclear relaxation and the vibrational contributions to the static molecular electrical properties, the vibrational Stark effect (VSE) and the vibrational intensity effect (VIE). From a mathematical point of view, when a static and uniform electric field is applied to a molecule, the energy of this system can be expressed in terms of a double power series with respect to the bond length and to the field strength. From the power series expansion of the potential energy, field-dependent expressions for the equilibrium geometry, for the potential energy and for the force constant are obtained. The nuclear relaxation and vibrational contributions to the molecular electrical properties are analyzed in terms of the derivatives of the electronic molecular properties. In general, the results presented show that accurate inclusion of the correlation energy and large basis sets are needed to calculate the molecular electrical properties and their derivatives with respect to either nuclear displacements or/and field strength. With respect to experimental data, the calculated power series coefficients are overestimated by the SCF, CISD, and QCISD methods. On the contrary, perturbation methods (MP2 and MP4) tend to underestimate them. In average and using the 6-311 + G(3df) basis set and for the CO molecule, the nuclear relaxation and the vibrational contributions to the molecular electrical properties amount to 11.7%, 3.3%, and 69.7% of the purely electronic μ, α, and β values, respectively

The Energy metabolism of China and India between 1971-2010: studying the bifurcation

This paper presents a comparison of the changes in the energetic metabolic pattern of China and India, the two most populated countries in the world, with two economies undergoing an important economic transition. The comparison of the changes in the energetic metabolic pattern has the scope to characterize and explain a bifurcation in their evolutionary path in the recent years, using the Multi-Scale Integrated Analysis of Societal and Ecosystem Metabolism (MuSIASEM) approach. The analysis shows an impressive transformation of China’s energy metabolism determined by the joining of the WTO in 2001. Since then, China became the largest factory of the world with a generalized capitalization of all sectors ―especially the industrial sector― boosting economic labor productivity as well as total energy consumption. India, on the contrary, lags behind when considering these factors. Looking at changes in the household sector (energy metabolism associated with final consumption) in the case of China, the energetic metabolic rate (EMR) soared in the last decade, also thanks to a reduced growth of population, whereas in India it remained stagnant for the last 40 years. This analysis indicates a big challenge for India for the next decade. In the light of the data analyzed both countries will continue to require strong injections of technical capital requiring a continuous increase in their total energy consumption. When considering the size of these economies it is easy to guess that this may induce a dramatic increase in the price of energy, an event that at the moment will penalize much more the chance of a quick economic development of India.

Lipid (energy) reserves of european hake (Merluccius Merluccius) in the North-Western Mediterranean

This study analyses for the first time the lipid (energy) reserves of European hake (Merluccius merluccius) in the north-western Mediterranean from an ecophysiological perspective. Results show that there is a progressive accumulation of lipids in the liver of maturing hake -where the bulk of the fat is stored- as individuals grow. Results also indicate that female pre-spawners expend much energy on reproductive activities since they present lower liver lipid reserves than juveniles and maturing individuals. Furthermore, results show that female pre-spawners with higher lipid reserves in their livers had a higher amount of lipids in their ovaries, suggesting that maternal condition (spawner quality) may affect the reproductive potential of hake. Overall, the results of this study suggest that the analysis of liver lipid reserves during pre-spawning, along with the evaluation of the gonadosomatic index and the consideration of the reproductive stage, can contribute to improve the estimation of the reproductive potential of gadoid species such as hake

Basis set effects on the energy and hardness profiles of the hydrogen fluoride dimer

In earlier work, the present authors have shown that hardness profiles are less dependent on the level of calculation than energy profiles for potential energy surfaces (PESs) having pathological behaviors. At variance with energy profiles, hardness profiles always show the correct number of stationary points. This characteristic has been used to indicate the existence of spurious stationary points on the PESs. In the present work, we apply this methodology to the hydrogen fluoride dimer, a classical difficult case for the density functional theory methods

Energy Management for Stand-Alone Renewable Energy Systems (E-MAN-RES). Simulacions de sistemes.

L’objecte del present informe és la descripció dels treballs duts a terme en l’Activitat 2 del projecte E-MAN-RES: models de simulació i càlcul per optimització i anàlisi de sensibilitat de la gestió de la demanda, per part de la Universitat Politècnica de Catalunya.