VO: a strongly correlated metal close to a Mott-Hubbard transition

Here, we present experimental and computational evidences to support that rocksalt cubic VO is a strongly correlated metal with non-Fermi-liquid thermodynamics and an unusually strong spin-lattice coupling. An unexpected change of sign of metallic thermopower with composition is tentatively ascribed to the presence of a pseudogap in the density of states. These properties are discussed as signatures of the proximity to a magnetic quantum phase transition. The results are summarized in an electronic phase diagram for the 3d monoxides, which resembles that of other strongly correlated systems. The structural and electronic simplicity of 3d monoxides makes them ideal candidates to progress in the understanding of highly correlated electron systems.

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.

Theoretical insights on electron donor-acceptor interactions involving carbon dioxide

Electron donor-acceptor (EDA) interactions are widely involved in chemistry and their understanding is essential to design new technological applications in a variety of fields ranging from material sciences and chemical engineering to medicine. In this work, we study EDA complexes of carbon dioxide with ketones using several ab initio and Density Functional Theory methods. Energy contributions to the interaction energy have been analyzed in detail using both variational and perturbational treatments. Dispersion energy has been shown to play a key role in explaining the high stability of a non-conventional structure, which can roughly be described by a cooperative EDA interaction.

Non-parametrized functionals with empirical dispersion corrections: A happy match?

The performances of two parametrized functionals (namely B3LYP and B2PYLP) have been compared with those of two non-parametrized functionals (PBE0 and PBE0-DH) on a relatively large benchmark set when three different types of dispersion corrections are applied [namely the D2, D3 and D3(BJ) models]. Globally, the MAD computed using non-parametrized functionals decreases when adding dispersion terms although the accuracy not necessarily increases with the complexity of the model of dispersion correction used. In particular, the D2 correction is found to improve the performances of both PBE0 and PBE0-DH, while no systematic improvement is observed going from D2 to D3 or D3(BJ) corrections. Indeed when including dispersion, the number of sets for which PBE0-DH is the best performing functional decreases at the benefit of B2PLYP. Overall, our results clearly show that inclusion of dispersion corrections is more beneficial to parametrized double-hybrid functionals than to non-parametrized ones. The same conclusions globally hold for the corresponding global hybrids, showing that the marriage between non-parametrized functionals and empirical corrections may be a difficult deal.

Role of potassium orbitals in the metallic behavior of K3picene

Detailed electronic structure calculations of picene clusters doped by potassium modeling the crystalline K3picene structure show that while two electrons are completely transferred from potassium atoms to the lowest-energy unoccupied molecular orbital of pristine picene, the third one remains closely attached to both material components. Multiconfigurational analysis is necessary to show that many structures of almost degenerate total energies compete to define the cluster ground state. Our results prove that the 4s orbital of potassium should be included in any interaction model describing the material. We propose a quarter-filled two-orbital model as the most simple model capable of describing the electronic structure of K-intercalated picene. Precise solutions obtained by a development of the Lanczos method show low-energy electronic excitations involving orbitals located at different positions. Consequently, metallic transport is possible in spite of the clear dominance of interaction over hopping.

Luminosity dependent accretion state change in GRO J1008–57

In a former publication, we have analyzed the transient neutron star X-ray binary GRO J1008–57 using all available RXTE-, Swift-, and Suzaku-data. As we have found, the source’s spectral components, i.e., a power-law with high exponential cutoff and a black-body, are strongly correlated with the hard X-ray flux (15–50 keV). We update the analytical description of these dependence, including a change in the photon index behaviour from a flat to a logarithmic function. The flux, where the change occurs, is consistent with the onset of the black-body emission. Thus, a change of the accretion state always occurs in GRO J1008–57 at a particular flux level.

Theoretical Rationalization of the Singlet–Triplet Gap in OLEDs Materials: Impact of Charge-Transfer Character

New materials for OLED applications with low singlet–triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet–triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet–triplet transition. Finally, we quantitatively correlate the singlet–triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

Accurate Treatment of Large Supramolecular Complexes by Double-Hybrid Density Functionals Coupled with Nonlocal van der Waals Corrections

In this work, we present a thorough assessment of the performance of some representative double-hybrid density functionals (revPBE0-DH-NL and B2PLYP-NL) as well as their parent hybrid and GGA counterparts, in combination with the most modern version of the nonlocal (NL) van der Waals correction to describe very large weakly interacting molecular systems dominated by noncovalent interactions. Prior to the assessment, an accurate and homogeneous set of reference interaction energies was computed for the supramolecular complexes constituting the L7 and S12L data sets by using the novel, precise, and efficient DLPNO-CCSD(T) method at the complete basis set limit (CBS). The correction of the basis set superposition error and the inclusion of the deformation energies (for the S12L set) have been crucial for obtaining precise DLPNO-CCSD(T)/CBS interaction energies. Among the density functionals evaluated, the double-hybrid revPBE0-DH-NL and B2PLYP-NL with the three-body dispersion correction provide remarkably accurate association energies very close to the chemical accuracy. Overall, the NL van der Waals approach combined with proper density functionals can be seen as an accurate and affordable computational tool for the modeling of large weakly bonded supramolecular systems.

An hybrid parallel algorithm for solving tridiagonal linear systems versus the Wang’s method in a Cray T3D BSP computer

In this paper we describe an hybrid algorithm for an even number of processors based on an algorithm for two processors and the Overlapping Partition Method for tridiagonal systems. Moreover, we compare this hybrid method with the Partition Wang’s method in a BSP computer. Finally, we compare the theoretical computation cost of both methods for a Cray T3D computer, using the cost model that BSP model provides.

A parallel method for impulsive image noise removal on hybrid CPU/GPU systems

A parallel algorithm for image noise removal is proposed. The algorithm is based on peer group concept and uses a fuzzy metric. An optimization study on the use of the CUDA platform to remove impulsive noise using this algorithm is presented. Moreover, an implementation of the algorithm on multi-core platforms using OpenMP is presented. Performance is evaluated in terms of execution time and a comparison of the implementation parallelised in multi-core, GPUs and the combination of both is conducted. A performance analysis with large images is conducted in order to identify the amount of pixels to allocate in the CPU and GPU. The observed time shows that both devices must have work to do, leaving the most to the GPU. Results show that parallel implementations of denoising filters on GPUs and multi-cores are very advisable, and they open the door to use such algorithms for real-time processing.

Reverse Geometry Hybrid Contact Lens Fitting in a Case of Donor-Host Misalignment after Keratoplasty

Purpose: To report the successful outcome obtained after fitting a new hybrid contact lens in a cornea with an area of donor-host misalignment and significant levels of irregular astigmatism after penetrating keratoplasty (PKP). Materials and methods: A 41-year-old female with bilateral asymmetric keratoconus underwent PKP in her left eye due to the advanced status of the disease. One year after surgery, the patient referred a poor visual acuity and quality in this eye. The fitting of different types of rigid gas permeable contact lenses was performed, but with an unsuccessful outcome due to contact lens stability problems and uncomfortable wear. Scheimpflug imaging evaluation revealed that a donor-host misalignment was present at the nasal area. Contact lens fitting with a reverse geometry hybrid contact lens (Clearkone, SynergEyes Carlsbad) was then fitted. Visual, refractive, and ocular aberrometric outcomes were evaluated during a 1-year period after the fitting. Results: Uncorrected distance visual acuity improved from a prefitting value of 20/200 to a best corrected postfitting value of 20/20. Prefitting manifest refraction was +5.00 sphere and -5.50 cylinder at 75°, with a corrected distance visual acuity of 20/30. Higher order root mean square (RMS) for a 5 mm pupil changed from a prefitting value of 6.83 µm to a postfitting value of 1.57 µm (5 mm pupil). The contact lens wearing was referred as comfortable, with no anterior segment alterations. Conclusion: The SynergEyes Clearkone contact lens seems to be another potentially useful option for the visual rehabilitation after PKP, especially in cases of donor-host misalignment.