First theoretical probe for alkynyl bridged thiophene modified coumarin nonlinear optical materials with D-π-A and A-π-D-π-A structures

First-principles exploration is very important to molecular design. In this study, geometric structure, intramolecular charge transfer (ICT), energy levels, polar moment, and ultraviolet–visible (UV–Vis) spectroscopy of eight novel and different alkynyl bridged thiophene modified coumarin nonlinear optical molecules with [Formula: see text]-[Formula: see text]-[Formula: see text] and [Formula: see text]-[Formula: see text]-[Formula: see text]-[Formula: see text]-[Formula: see text] structures had been studied by density-functional theory (DFT) calculations within B3LYP hybrid functional using 6-31 [Formula: see text], [Formula: see text] Gaussian type molecular-orbital basis set. This has guiding significance for the design of nonlinear optical molecules and the development of coumarin-based photoelectric molecules.

Chalcogen···Chalcogen Bonding in Molybdenum Disulfide, Molybdenum Diselenide and Molybdenum Ditelluride Dimers as Prototypes for a Basic Understanding of the Local Interfacial Chemical Bonding Environment in 2D Layered Transition Metal Dichalcogenides

An attempt was made, using computational methods, to understand whether the intermolecular interactions in the dimers of molybdenum dichalcogenides MoCh2 (Ch = chalcogen, element of group 16, especially S, Se and Te) and similar mixed-chalcogenide derivatives resemble the room temperature experimentally observed interactions in the interfacial regions of molybdenites and their other mixed-chalcogen derivatives. To this end, MP2(Full)/def2-TVZPPD level electronic structure calculations on nine dimer systems, including (MoCh2)2 and (MoChCh′2)2 (Ch, Ch′ = S, Se and Te), were carried out not only to demonstrate the energetic stability of these systems in the gas phase, but also to reproduce the intermolecular geometrical properties that resemble the interfacial geometries of 2D layered MoCh2 systems reported in the crystalline phase. Among the six DFT functionals (single and double hybrids) benchmarked against MP2(full), it was found that the double hybrid functional B2PLYPD3 has some ability to reproduce the intermolecular geometries and binding energies. The intermolecular geometries and binding energies of all nine dimers are discussed, together with the charge density topological aspects of the chemical bonding interactions that emerge from the application of the quantum theory of atoms in molecules (QTAIM), the isosurface topology of the reduced density gradient noncovalent index, interaction region indicator and independent gradient model (IGM) approaches. While the electrostatic surface potential model fails to explain the origin of the S···S interaction in the (MoS2)2 dimer, we show that the intermolecular bonding interactions in all nine dimers examined are a result of hyperconjugative charge transfer delocalizations between the lone-pair on (Ch/Ch′) and/or the π-orbitals of a Mo–Ch/Ch′ bond of one monomer and the dπ* anti-bonding orbitals of the same Mo–Ch/Ch′ bond in the second monomer during dimer formation, and vice versa. The HOMO–LUMO gaps calculated with the MN12-L functional were 0.9, 1.0, and 1.1 eV for MoTe2, MoSe2 and MoS2, respectively, which match very well with the solid-state theoretical (SCAN-rVV10)/experimental band gaps of 0.75/0.88, 0.90/1.09 and 0.93/1.23 eV of the corresponding systems, respectively. We observed that the gas phase dimers examined are perhaps prototypical for a basic understanding of the interfacial/inter-layer interactions in molybdenum-based dichalcogenides and their derivatives.

First-principles study of the structural and thermoelectric properties of Y-doped α-SrSi2

The narrow-gap semiconductor α-SrSi2 is a promising candidate for low-temperature thermoelectric applications with low environmental load. The only experimental report in which α-SrSi2 is reported to have n-type conductivity is one where it had been doped with yttrium. To further clarify the effects of impurities, theoretical studies are needed. The α-SrSi2 has a very narrow band gap (~13–35 meV), causing difficulties in the accurate calculation of the electronic and thermoelectric properties. In our previous study, we overcame this problem for undoped α-SrSi2 using hybrid functional theory. We used this method in this study to investigate the structures, energetic stabilities, electronic structures, and thermoelectric properties of Y-doped α-SrSi2. The results indicate that substitution at Sr-sites is energetically about two times more stable than that at Si-sites. Furthermore, negative Seebeck coefficients were obtained at low temperatures and reverted to p-type with increasing temperature, which is consistent with the experimental results.

Defect Calculation by Combined SCAN and Hybrid Functional in γ-CsPbI3

γ-CsPbI3 solar cells have achieved promising efficiencies, yet the quantitative understanding of their defect properties is limited due to severe computational challenges of hybrid functionals. We have discovered an algorithm...

Antioxidant Activity of Eugenol And Its Acetyl And Nitroderivatives: A DFT Approach of DPPH Test.

This work evaluates the antioxidant potential of acetyl and nitro derivatives of eugenol through computational techniques. Structural analysis and Hydrogen Atomic Transfer (HAT) antioxidant mechanism were investigated by density functional theory (DFT). Each molecular structure was optimized by the hybrid functional M06-2X with a basis set 6-31+G(d,p), and the HAT mechanism with HO, HOO, CH3O, DPPH radicals was evaluated. In agreement with experimental data from previous studies, two steps of hydrogen transfer were tested. Thermodynamic data showed the need for two stages of hydrogen transfer, followed by the formation of quinones to make the reaction with DPPH spontaneous. Theoretical kinetic data showed that the preferred antioxidant site depends on the instability of the attacking radical and confirmed the antioxidant profile of eugenol (E1) and 5-allyl-3-nitrobenzene-1,2-diol (E5) in the DPPH test. This study shows that the 4-allyl-2-methoxy-(4-nitrophenol) (E4) structure also has an anti-radical activity that is not seen in the experimental due to chemoselectivity of DPPH.

The GW Miracle in Many-Body Perturbation Theory for the Ionization Potential of Molecules

We use the GW100 benchmark set to systematically judge the quality of several perturbation theories against high-level quantum chemistry methods. First of all, we revisit the reference CCSD(T) ionization potentials for this popular benchmark set and establish a revised set of CCSD(T) results. Then, for all of these 100 molecules, we calculate the HOMO energy within second and third-order perturbation theory (PT2 and PT3), and, GW as post-Hartree-Fock methods. We found GW to be the most accurate of these three approximations for the ionization potential, by far. Going beyond GW by adding more diagrams is a tedious and dangerous activity: We tried to complement GW with second-order exchange (SOX), with second-order screened exchange (SOSEX), with interacting electron-hole pairs (WTDHF), and with a GW density-matrix (γGW). Only the γGW result has a positive impact. Finally using an improved hybrid functional for the non-interacting Green’s function, considering it as a cheap way to approximate self-consistency, the accuracy of the simplest GW approximation improves even more. We conclude that GW is a miracle: Its subtle balance makes GW both accurate and fast.

The Halogenation Effects of Electron Acceptor ITIC for Organic Photovoltaic Nano-Heterojunctions

Molecular engineering plays a critical role in the development of electron donor and acceptor materials for improving power conversion efficiency (PCE) of organic photovoltaics (OPVs). The halogenated acceptor materials in OPVs have shown high PCE. Here, to investigate the halogenation mechanism and the effects on OPV performances, based on the density functional theory calculations with the optimally tuned screened range-separated hybrid functional and the consideration of solid polarization effects, we addressed the halogenation effects of acceptor ITIC, which were modeled by bis-substituted ITIC with halogen and coded as IT-2X (X = F, Cl, Br), and PBDB-T:ITIC, PBDB-T:IT-2X (X = F, Cl, Br) complexes on their geometries, electronic structures, excitations, electrostatic potentials, and the rate constants of charge transfer, exciton dissociation (ED), and charge recombination processes at the heterojunction interface. The results indicated that halogenation of ITIC slightly affects molecular geometric structures, energy levels, optical absorption spectra, exciton binding energies, and excitation properties. However, the halogenation of ITIC significantly enlarges the electrostatic potential difference between the electron acceptor and donor PBDB-T with the order from fluorination and chlorination to bromination. The halogenation also increases the transferred charges of CT states for the complexes. Meanwhile, the halogenation effects on CT energies and electron process rates depend on different haloid elements. No matter which kinds of haloid elements were introduced in the halogenation of acceptors, the ED is always efficient in these OPV devices. This work provides an understanding of the halogenation mechanism, and is also conducive to the designing of novel materials with the aid of the halogenation strategy.

Novel Janus group III chalcogenide monolayers Al2XY2 (X/Y= S, Se, Te): First-principles insight onto the structural, electronic, and transport properties

Motivated by the recent successful synthesis of 2D quintuple-layer atomic materials, for the first time, we design and investigate the electronic and transport properties of Janus Al$_2XY_2$ ($X/Y =$ S, Se, Te; $X \neq Y$) monolayers by using the density functional theory. Our calculations demonstrate that most of the models of Al$_2XY_2$ (except for Al$_2$STe$_2$ monolayer) are dynamically and mechanically stable. By using the hybrid functional, all models of Al$_2XY_2$ are semiconductors with an indirect bandgap. Meanwhile, Al$_2$TeS$_2$ monolayer is found to be metal at the PBE level. Due to the vertical asymmetry structure, an intrinsic built-in electric field exists in the Al$_2XY_2$ and leads to a difference in the vacuum levels between the two sides of the monolayers. Carrier mobilities of Al$_2XY_2$ monolayers are high directional anisotropic due to the anisotropy of their deformation potential constant. Al$_2XY_2$ monolayers exhibit high electron mobility, particularly, the electron mobility of Al$_2$SeS$_2$ exceeds $1\times 10^4$~cm$^2$/Vs, suggesting that they are suitable for applications in nanometer sized electronic devices.