Double Hybrid Functionals and the Π-System Bond Length Alternation Challenge: Rivaling Accuracy of Post-HF Methods

Predicting accurate bond length alternations (BLAs) in long conjugated oligomers has been a significant challenge for electronic-structure methods for many decades, made particularly important by the close relationships between BLA and the rich optoelectronic properties of π-delocalized systems. Here, we test the accuracy of recently developed, and increasingly popular, double hybrid (DH) functionals, positioned at the top of Jacobs Ladder of DFT methods of increasing sophistication, computational cost, and accuracy, due to incorporation of MP2 correlation energy. Our test systems comprise oligomeric series of polyacetylene, polymethineimine, and polysilaacetylene up to six units long. MP2 calculations reveal a pronounced shift in BLAs between the 6-31G(d) basis set used in many studies of BLA to date and the larger cc-pVTZ basis set, but only modest shifts between cc-pVTZ and aug-cc-pVQZ results. We hence perform new reference CCSD(T)/cc-pVTZ calculations for all three series of oligomers against which we assess the performance of several families of DH functionals based on BLYP, PBE, and TPSS, along with lower-rung relatives including global- and range-separated hybrids. Our results show that DH functionals systematically improve the accuracy of BLAs relative to single hybrid functionals. xDH-PBE0 (N4 scaling using SOS-MP2) emerges as a DH functional rivaling the BLA accuracy of SCS-MP2 (N5 scaling), which was found to offer the best compromise between computational cost and accuracy the last time the BLA accuracy of DFT- and wave function-based methods was systematically investigated. Interestingly, xDH-PBE0 (XYG3), which differs to other DHs in that its MP2 term uses PBE0 (B3LYP) orbitals that are not self-consistent with the DH functional, is an outlier of trends of decreasing average BLA errors with increasing fractions of MP2 correlation and HF exchange.

Correlation of the liquid–liquid equilibrium data for specific ternary systems with one or two partially miscible binary subsystems

This paper presents the results of a liquid–liquid equilibrium data correlation for 11 ternary systems which have not been previously fitted using the NRTL model or, when they have, the results presented in the literature are inconsistent with the experimental behavior of the system. These ternary systems include mixtures with one or two partially miscible pairs. During the correlation process, new restrictions were imposed on the values for the NRTL binary parameters to ensure correct prediction of the total or partial miscibility for the binary pairs involved. In addition, topological concepts related to the Gibbs stability test have been applied in order to validate the results in the whole range of compositions.

Exponential decay of spin-spin correlation between distant defect states produced by contour hydrogenation of polycyclic aromatic hydrocarbon molecules

The first few low-lying spin states of alternant polycyclic aromatic hydrocarbon (PAH) molecules of several shapes showing defect states induced by contour hydrogenation have been studied both by ab initio methods and by a precise numerical solution of Pariser-Parr-Pople (PPP) interacting model. In accordance with Lieb's theorem, the ground state shows a spin multiplicity equal to one for balanced molecules, and it gets larger values for imbalanced molecules (that is, when the number of π electrons on both subsets is not equal). Furthermore, we find a systematic decrease of the singlet-triplet splitting as a function of the distance between defects, regardless of whether the ground state is singlet or triplet. For example, a splitting smaller than 0.001 eV is obtained for a medium size C46H28 PAH molecule (di-hydrogenated [11]phenacene) showing a singlet ground state. We conclude that π electrons unbound by lattice defects tend to remain localized and unpaired even when long-range Coulomb interaction is taken into account. Therefore they show a biradical character (polyradical character for more than two defects) and should be studied as two or more local doublets. The implications for electron transport are potentially important since these unpaired electrons can trap traveling electrons or simply flip their spin at a very small energy cost.

No anticorrelation between cyclotron line energy and X-ray flux in 4U 0115+634

We report on an outburst of the high mass X-ray binary 4U 0115+634 with a pulse period of 3.6 s in 2008 March/April as observed with RXTE and INTEGRAL. During the outburst the neutron star’s luminosity varied by a factor of 10 in the 3–50 keV band. In agreement with earlier work we find evidence of five cyclotron resonance scattering features at ~10.7, 21.8, 35.5, 46.7, and 59.7 keV. Previous work had found an anticorrelation between the fundamental cyclotron line energy and the X-ray flux. We show that this apparent anticorrelation is probably due to the unphysical interplay of parameters of the cyclotron line with the continuum models used previously, e.g., the negative and positive exponent power law (NPEX). For this model, we show that cyclotron line modeling erroneously leads to describing part of the exponential cutoff and the continuum variability, and not the cyclotron lines. When the X-ray continuum is modeled with a simple exponentially cutoff power law modified by a Gaussian emission feature around 10 keV, the correlation between the line energy and the flux vanishes, and the line parameters remain virtually constant over the outburst. We therefore conclude that the previously reported anticorrelation is an artifact of the assumptions adopted in the modeling of the continuum.

Gibbs Energy of Mixing Function: Topological Analysis in Azeotropic Systems

ESAT 2014. 27th European Symposium on Applied Thermodynamics, Eindhoven University of Technology, July 6-9, 2014.

Energy consumption in an urban wastewater treatment plant: the case of Murcia Region (Spain)

Of all the costs associated with the operation and maintenance of wastewater treatment plants (WWTPs), those associated with energy use tend to be the most significant. From this point of view, it is hence logical that energy efficiency and saving strategies should be one of the current focuses of debate amongst those involved with the management of WWTPs. The present study's objective is to determine the correlation between size and energy consumption for a WWTP. To this end, 90 WWTPs currently in service were analysed and their energetic impact quantified in terms of kWh/m3 of water treated. The results obtained demonstrate that energy consumption ratio increases as the size of WWTPs decreases, either in terms of treatment volume or population equivalent served.