Juan Maria García Lastra

Orbital-free effective embedding potential at nuclear cusps

A strategy to construct approximants to the kinetic-energy-functional dependent component (v(t)[rho(A),rho(B)](r)) of the effective potential in one-electron equations for orbitals embedded in a frozen-density environment [Eqs. (20) and (21) in Wesolowski and Warshel, J. Phys. Chem. 97, (1993) 8050] is proposed. In order to improve the local behavior of the orbital-free effective embedding potential near nuclei in the environment, the exact behavior of v(t)[rho(A),rho(B)](r) at rho(A)-->0 and integralrho(B)dr=2 is taken into account. As a result, the properties depending on the quality of this potential are invariably improved compared to the ones obtained using conventional approximants which violated the considered exact condition. The approximants obtained following the proposed strategy and especially the simplest one constructed in this work are nondecomposable, i.e., cannot be used to obtain the analytic expression for the functional of the total kinetic energy.

Quantization of Hall Resistance at the Metallic Interface between an Oxide Insulator and SrTiO_{3}.

The two-dimensional metal forming at the interface between an oxide insulator and SrTiO_{3} provides new opportunities for oxide electronics. However, the quantum Hall effect, one of the most fascinating effects of electrons confined in two dimensions, remains underexplored at these complex oxide heterointerfaces. Here, we report the experimental observation of quantized Hall resistance in a SrTiO_{3} heterointerface based on the modulation-doped amorphous-LaAlO_{3}/SrTiO_{3} heterostructure, which exhibits both high electron mobility exceeding 10,000  cm^{2}/V s and low carrier density on the order of ∼10^{12}  cm^{-2}. Along with unambiguous Shubnikov-de Haas oscillations, the spacing of the quantized Hall resistance suggests that the interface is comprised of a single quantum well with ten parallel conducting two-dimensional sub-bands. This provides new insight into the electronic structure of conducting oxide interfaces and represents an important step towards designing and understanding advanced oxide devices.

Effect of Sb Segregation on Conductance and Catalytic Activity at Pt/Sb-Doped SnO2 Interface: A Synergetic Computational and Experimental Study

Antimony-doped tin dioxide (ATO) is considered a promising support material for Pt-based fuel cell cathodes, displaying enhanced stability over carbon-based supports. In this work, the effect of Sb segregation on the conductance and catalytic activity at Pt/ATO interface was investigated through a combined computational and experimental study. It was found that Sb-dopant atoms prefer to segregate toward the ATO/Pt interface. The deposited Pt catalysts, interestingly, not only promote Sb segregation, but also suppress the occurrence of Sb(3+) species, a charge carrier neutralizer at the interface. The conductivity of ATO was found to increase, to a magnitude close to that of activated carbon, with an increment of Sb concentration before reaching a saturation point around 10%, and then decrease, indicating that Sb enrichment at the ATO surface may not always favor an increment of the electric current. In addition, the calculation results show that the presence of Sb dopants in ATO has little effect on the catalytic activity of deposited three-layer Pt toward the oxygen reduction reaction, although subsequent alloying of Pt and Sb could lower the corresponding catalytic activity. These findings help to support future applications of ATO/Pt-based materials as possible cathodes for proton exchange membrane fuel cell applications with enhanced durability under practical applications.

Machine learning-based screening of complex molecules for polymer solar cells

Polymer solar cells admit numerous potential advantages including low energy payback time and scalable high-speed manufacturing, but the power conversion efficiency is currently lower than for their inorganic counterparts. In a Phenyl-C_61-Butyric-Acid-Methyl-Ester (PCBM)-based blended polymer solar cell, the optical gap of the polymer and the energetic alignment of the lowest unoccupied molecular orbital (LUMO) of the polymer and the PCBM are crucial for the device efficiency. Searching for new and better materials for polymer solar cells is a computationally costly affair using density functional theory (DFT) calculations. In this work, we propose a screening procedure using a simple string representation for a promising class of donor-acceptor polymers in conjunction with a grammar variational autoencoder. The model is trained on a dataset of 3989 monomers obtained from DFT calculations and is able to predict LUMO and the lowest optical transition energy for unseen molecules with mean absolute errors of 43 and 74 meV, respectively, without knowledge of the atomic positions. We demonstrate the merit of the model for generating new molecules with the desired LUMO and optical gap energies which increases the chance of finding suitable polymers by more than a factor of five in comparison to the randomised search used in gathering the training set.

Combined DFT and Differential Electrochemical Mass Spectrometry Investigation of the Effect of Dopants in Secondary Zinc-Air Batteries

Zinc-air batteries offer the potential of low-cost energy storage with high specific energy, but at present secondary Zn-air batteries suffer from poor cyclability. To develop economically viable secondary Zn-air batteries, several properties need to be improved: choking of the cathode, catalyzing the oxygen evolution and reduction reactions, limiting dendrite formation and suppressing the hydrogen evolution reaction (HER). Understanding and alleviating HER at the negative electrode in a secondary Zn-air battery is a substantial challenge, for which it is necessary to combine computational and experimental research. Here, we combine differential electrochemical mass spectrometry (DEMS) and density functional theory (DFT) calculations to investigate the fundamental role and stability when cycling in the presence of selected beneficial additives, that is, In and Bi, and Ag as a potentially unfavorable additive. We show that both In and Bi have the desired property for a secondary battery, that is, upon recharging they will remain on the surface, thereby retaining the beneficial effects on Zn dissolution and suppression of HER. This is confirmed by DEMS, where it is observed that In reduces HER and Bi affects the discharge potential beneficially compared to a battery without additives. Using a simple procedure based on adsorption energies calculated with DFT, it is found that Ag suppresses OH adsorption, but, unlike In and Bi, it does not hinder HER. Finally, it is shown that mixing In and Bi is beneficial compared to the additives by themselves as it improves the electrochemical performance and cyclic stability of the secondary Zn-air battery.Zinc-air batteries offer the potential of low cost energy storage with high specific energy, but at present secondary Zn-air batteries suffer from poor cyclability. To develop economically viable secondary Znair batteries, several properties need to be improved: choking of the cathode, catalyzing the oxygen evolution and reduction reactions, limiting dendrite formation and suppressing the hydrogen evolution reaction (HER). Understanding and alleviating HER at the negative electrode in a secondary Zn-air battery is a substantial challenge, where it is necessary to combine computational and experimental research. Here, we combine Differential Electrochemical Mass Spectrometry (DEMS) and density functional theory (DFT) calculations to investigate the fundamental role and stability over cycling of selected beneficial additives, i.e. In and Bi, and Ag as a potentially unfavorable additive. We show that both In and Bi have the desired property for a secondary battery that upon recharging, they will remain in the surface, thereby retaining the beneficial effects on Zn dissolution and suppression of HER. This is confirmed by DEMS, where we observe that In lowers HER and Bi affects the discharge potential beneficially, compared to a battery without additives. Using a simple procedure based on adsorption energies calculated with DFT, we find that Ag suppress OH adsorption but, unlike In and Bi, does not hinder HER. Finally, it is shown that mixing In and Bi is beneficial compared to the additives by themselves, as it improves the electrochemical performance and cyclic stability of the secondary Zn-air

Frequency- and temperature-dependent dielectric response in hybrid molecular beam epitaxy-grown BaSnO3 films

We report on the dielectric response of epitaxial BaSnO3 films grown on Nb-doped SrTiO3 (001) substrates using a hybrid molecular beam epitaxy approach. Metal-insulator-metal capacitors were fabricated to obtain frequency- and temperature-dependent dielectric constant and loss. Irrespective of film thickness and cation stoichiometry, the dielectric constant obtained from Ba1−xSn1−yO3 films remained largely unchanged at 15-17 and was independent of frequency and temperature. A loss tangent of ∼1 × 10−3 at 1 kHz < f < 100 kHz was obtained for stoichiometric films, which increased significantly with non-stoichiometry. Using density functional theory calculations, these results are discussed in the context of point defect complexes that can form during film synthesis.We report on the dielectric response of epitaxial BaSnO3 films grown on Nb-doped SrTiO3 (001) substrates using a hybrid molecular beam epitaxy approach. Metal-insulator-metal capacitors were fabricated to obtain frequency- and temperature-dependent dielectric constant and loss. Irrespective of film thickness and cation stoichiometry, the dielectric constant obtained from Ba1−xSn1−yO3 films remained largely unchanged at 15-17 and was independent of frequency and temperature. A loss tangent of ∼1 × 10−3 at 1 kHz < f < 100 kHz was obtained for stoichiometric films, which increased significantly with non-stoichiometry. Using density functional theory calculations, these results are discussed in the context of point defect complexes that can form during film synthesis.