Computerized implementation of higher‐order electron‐correlation methods and their linear‐scaling divide‐and‐conquer extensions

We have implemented a linear‐scaling divide‐and‐conquer (DC)‐based higher‐order coupled‐cluster (CC) and Møller–Plesset perturbation theories (MPPT) as well as their combinations automatically by means of the tensor contraction engine, which is a computerized symbolic algebra system. The DC‐based energy expressions of the standard CC and MPPT methods and the CC methods augmented with a perturbation correction were proposed for up to high excitation orders [e.g., CCSDTQ, MP4, and CCSD(2)_TQ]. The numerical assessment for hydrogen halide chains, polyene chains, and first coordination sphere (C1) model of photoactive yellow protein has revealed that the DC‐based correlation methods provide reliable correlation energies with significantly less computational cost than that of the conventional implementations. © 2017 Wiley Periodicals, Inc.     

Positronium formation cross-sections in the ground and excited states ( levels) in an -He atom collision

The positronium formation cross-sections in the ground and excited n=2 levels have been studied in an -He atom collision in the framework of eikonal approximation. Both the differential and total formation cross-sections have been investigated in the intermediate- and high-energy regime. Present eikonal results are found to differ appreciably from the corresponding first Born values even at very high incident energies. The total cross-section results have been compared with available experiments due to different groups as well as with other existing theoretical results. Received: 20 July 1998 / Received in final form: 5 January 1999     

Diode rectification and negative differential resistance of dipyrimidinyl–diphenyl molecular junctions

Addressable Au/dipyrimidinyl–diphenyl/Au molecular junctions are fabricated using elastic polymer stamp-printing method. To study the charge transport, current–voltage measurements are carried out from 95 up to 295 K in vacuum under both dark and light conditions. Reversible diode rectification and negative differential resistance phenomena are observed. The rectification efficiency dramatically decreases upon temperature increase or light illumination. Theoretical calculations based on the non-equilibrium Green’s function method combined with the density functional theory is performed to elucidate the negative differential resistance behaviors. We show that the different rectification efficiency is caused by the interfacial asymmetry and the dipole effects. The negative differential resistance may be attributed to the variation of the coupling degree between the incident states of the Au electrodes and the molecular orbitals, which depends largely on the S–Au contact geometry. The direct tunneling and Fowler–Nordheim tunneling act as the main transport mechanisms for low and high bias regions, respectively. The barrier height depends largely on the light illumination, substrate temperature, and bias polarity. The distinctly different adsorbing nature of the Au/molecule interface may account for the performances.     

Percolative charge transport in a co-evaporated organic molecular mixture

Understanding the charge transport in molecular semiconductor mixtures remains challenging, largely due to the lack of a universal dependence of carrier mobility upon doping concentration. Here we demonstrate that it is feasible to use the percolation theory to explain the change of charge mobility in a model system of 4,4′-bis(carbazol-9-yl)-biphenyl (CBP) and tris-(8-hydroxyquinoline) aluminum (Alq₃) with various doping concentrations. As the fraction of CBP within the mixtures increases, the charge mobility firstly shows a reduction at low CBP fraction due to the scattering effect, and then increases well following a percolation model. Electron microscopy and atomic force microscopy analysis suggest that CBP and Alq₃ are homogeneously mixed in their co-evaporated amorphous films, which meets the precondition for using percolation theory. We describe the possible microcosmic percolating mechanism with a model combining bond percolation with charge transfer integral calculation. Based on this model, the percolation threshold in molecular semiconductor mixtures can be predicated. For the hole and electron transport in our system, the predicated percolation thresholds are very close to the experimental values.     

Thermodynamic vs. kinetic control of excited-state proton transfer reactions

The “Excited-State Intramolecular Proton Transfer” (ESIPT) reactions in a number of organic fluorophores are among the fastest basic chemical reactions known so far and their rates can be observed even on femtosecond time scale. Accordingly, the reactant concentration, as monitored by its emission, should be negligibly small. In sharp contrast to this conventional wisdom, however, the coexistence of the reactant and the product of this reaction is so frequently observed in condensed media. We then discuss two possible origins of these effects: when the ESIPT reaction is perturbed and hence is slow on the time scale of emission (kinetic control) or when the reverse reaction repopulating the reactant state is fast and leads to the excited-state equilibrium (thermodynamic control). Upon reviewing a great number of ESIPT prototypical systems, we summarize and discuss different criteria for distinguishing these cases based on the steady-state and time-resolved spectroscopic studies and derive correlations between reversibility of these reactions and the solvent-dependent effects observed in fluorescence spectra.     

Investigation of structural and optoelectronic properties of annealed nickel phthalocyanine thin films

Thin films of nickel phthalocyanine (NiPc) were prepared by thermal evaporation and the effects of annealing temperature on the structural and optical properties of the samples were studied using different analytical methods. Structural analysis showed that the grain size and crystallinity of NiPc films improved as annealing temperature increased from 25 to 150 °C. Also, maximum grain size (71.3 nm) was obtained at 150 °C annealing temperature. In addition, NiPc films annealed at 150 °C had a very smooth surface with an RMS roughness of 0.41 nm. Optical analysis indicated that band gap energy of films at different annealing temperatures varied in the range of 3.22–3.28 eV. Schottky diode solar cells with a structure of ITO/PEDOT:PSS/NiPc/Al were fabricated. Measurement of the dark current density–voltage (J–V) characteristics of diodes showed that the current density of films annealed at 150 °C for a given bias was greater than that of other films. Furthermore, the films revealed the highest rectification ratio (23.1) and lowest barrier height (0.84 eV) demonstrating, respectively, 23% and 11% increase compared with those of the deposited NiPc films. Meanwhile, photoconversion behavior of films annealed at 150 °C under illumination showed the highest short circuit current density (0.070 mA/cm²) and open circuit voltage of (0.55 V).     

Intermolecular charge-transfer complexes between chlorothiazide antihypertensive drug against iodine sigma and picric acid pi acceptors: DFT and molecular docking interaction study with Covid-19 protease

The interaction of chlorothiazide (CH) as donor (D) with picric acid (PA) and iodine (I₂) as π- and σ-acceptors (A), respectively, gives charge-transfer (CT) complexes as a final products. The reaction of donor and acceptors were studied spectrophotometrically. The complexes are generally of the n-π* and n-σ* types, with the ground state wave function primarily characterized by the non-bonding structure. For the micro determination of chlorothiazide using picric acid and iodine as acceptors, the ideal conditions encouraging the formation of complexes are thoroughly explored. It was discovered that the stoichiometry of the molecular structure is 1:1 (D:A). The equilibrium constant and the molar extinction coefficient were calculated using Benesi-Hildebrand and its modifications. DFT/TD-DFT calculations with B3LYP/LanL2DZ and 6-311G++ level of theory were used to provide comparable theoretical data along with electronic energy gap of HOMO→LUMO. Molecular docking calculations have been performed between CT complexes and Covid-19 protease (6LU7) to study the interaction between them and their inhibitory effect.     

Emerging materials for plasmon-assisted photoelectrochemical water splitting

Energy production and environmental pollution are the two major problems the world is facing today. The depletion of fossil fuels and the emission of harmful gases into the atmosphere leads to the research on clean and renewable energy sources. In this context, hydrogen is considered an ideal fuel to meet global energy needs. Presently, hydrogen is produced from fossil fuels. However, the most desirable way is from clean and renewable energy sources, like water and sunlight. Sunlight is an abundant energy source for energy harvesting and utilization. Recent studies reveal that photoelectrochemical (PEC) water splitting has promise for solar to hydrogen (STH) conversion over the widely tested photocatalytic approach since hydrogen and oxygen gases can be quantified easily in PEC. For designing light-absorbing materials, semiconductors are the primary choice that undergoes excitation upon solar light irradiation to produce excitons (electron-hole pairs) to drive the electrolysis. Visible light active semiconductors are attractive to achieve high solar to chemical fuel conversion. However, pure semiconductor materials are far from practical applications because of charge carrier recombination, poor light-harvesting, and electrode degradation. Various heteronanostructures by the integration of metal plasmons overcome these issues. The incorporation of metal plasmons gained significance for improving the PEC water splitting performance. This review summarizes the possible main mechanisms such as plasmon-induced resonance energy transfer (PIRET), hot electron injection (HEI), and light scatting/trapping. It also deliberates the rational design of plasmonic structures for PEC water splitting. Furthermore, this review highlights the advantages of plasmonic metal-supported photoelectrodes for PEC water splitting.