Abstract In this paper we present the implementation and benchmarking of a Time Dependent Density Functional Theory approach in conjunction with Double Hybrid (DH) functionals. We focused on analysis their performance for through space charge‐transfer (CT) excitations which are well known to be very problematic commonly used functionals, such as global hybrids.Two different families functionals were compared, each them containing pure, hybrid double‐hybrid functionals.The results obtained...

Abstract We investigate the performance of a set recently introduced range‐separated double‐hybrid functionals, namely ω B2‐PLYP, B2GP‐PLYP, RSX‐0DH, and RSX‐QIDH models for hard‐to‐calculate excitation energies. compare with parent (B2‐PLYP, PBE0‐DH, PBE‐QIDH) other (DSD‐PBEP86) as well some most widely employed hybrid functionals (B3LYP, PBE0, M06‐2X, B97X). For this purpose, we select number medium‐sized intra‐ inter‐molecular charge‐transfer excitations, which are known to be challenging...

On approaching the glass transition, microscopic kinetic unit spends increasing time rattling in cage of first neighbors, whereas its average escape time, structural relaxation τα, increases from a few picoseconds up to thousands seconds. A thorough study correlation between τα and amplitude, expressed by Debye–Waller factor, was carried out. Molecular-dynamics simulations both model polymer system binary mixture were performed varying temperature, density ρ, potential length consider as...

Double perovskite cobaltites were recently presented as promising cathode materials for solid oxide fuel cells. While an atomistic mechanism was proposed oxygen diffusion in this family of materials, no direct experimental proof has been so far. We report here the first study that directly compares and theoretical pathways oxide, namely double cobaltite compound, NdBaCo2O5+x. Model-free nuclear density maps are obtained from maximum entropy method combined with Rietveld refinement against...

Many organic reactions are characterized by a complex mechanism with variety of transition states and intermediates different chemical natures. Their correct accurate theoretical characterization critically depends on the accuracy computational method used. In this work, we study ambimodal cycloaddition five states, two intermediates, three products, ask whether density functional theory (DFT) can provide description type multifaceted reaction. Our work fills gap in that most systematic...

The scaling of slow structural relaxation with fast caged dynamics is seen in the molten salt Ca0.4K0.6(NO3)1.4 (CKN) over about 13 decades time. Glycerol has been analysed detail. In glycerol, short-time mean-square displacement , a measure dynamics, contributed by free volume. It that, order to see scaling, observation time must be shorter than time-scales processes. Systems both negligible (like CKN, glycerol and network glassformers) high van der Waals liquids polymers) pressure–energy...

Strain has been proposed as a potential tool to increase the oxygen ion conduction in oxides. Here we study by means of molecular dynamics simulations influence isotropic and biaxial strain on proton conductivity yttrium-doped barium zirconate examine whether similar occurs for hydrogen diffusion. Compressive pressure is indeed shown favour diffusion diminishing oxygen–oxygen distance without affecting symmetry. For moderate strain, effect observed i.e. slight under compressive strain. High...

The study of how both steric and electrostatic interactions affect the structure liquids formed by quasitetrahedral molecules has been undertaken in this work. We have studied trichlorobromomethane (CBrCl${}_{3}$) dibromodichloromethane (CBr${}_{2}$Cl${}_{2}$), displaying a dipole along their C${}_{3\mathrm{v}}$ C${}_{2\mathrm{v}}$ molecular symmetry axes, respectively. short-range order liquid state determined using neutron diffraction experiments that were modeled through reverse Monte...

Theoretical characterization of reactions complex molecules depends on providing consistent accuracy for the relative energies intermediates and transition states. Here we employ DLPNO-CCSD(T) method with core–valence correlation, large basis sets, extrapolation to CBS limit provide benchmark values Diels–Alder states leading competitive strained pentacyclic adducts. We then used those benchmarks test a diverse set wave function density functional methods absolute barrier heights these Our...

The correlation between the fast cage dynamics and structural relaxation is investigated in a model polymer system. It shown that vibration amplitude, as expressed by Debye–Waller factor, time τα collapse on single universal curve with simple analytic form when temperature, density, chain length monomer–monomer interaction potential are changed. For physical states same coincidence of mean-square displacement, intermediate scattering function non-Gaussian parameter observed wide window...

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Abstract The combination of a Monte Carlo (MC) sampling the configurational space with time dependent‐density functional theory (TD‐DFT) to estimate vertical excitations energies has been applied compute absorption spectra family merocyanine dyes in both their monomeric and dimeric forms. These results have compared those obtained using static DFT/TD‐DFT approach as well available experimental spectra. Though suffering limitations related use DFT TD‐DFT for this type systems, our data...

Density-functional theory calculations are performed to investigate proton transport in BaSnO3. Structural optimizations the stable and saddle point configurations for transfer (hopping) reorientation allow description of high-temperature classical semi-classical regimes, which diffusion occurs by over-barrier motion. At lower temperature (typically below 300 K), we describe thermally-assisted quantum regime, protonic motion is nature "coincidence" favored thermal fluctuations surrounding...

HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not.The documents may come from teaching institutions in France abroad, public private centers.L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de scientifiques niveau recherche, publiés ou non, émanant des établissements d'enseignement recherche français étrangers, laboratoires publics privés. Synergistic effect...

Among promising applications, LiKCO3 can be used as component of the oxide–carbonate electrolytes for low-temperature solid oxide fuel cells (LT-SOFCs), but species ensuring transport at interface between two phases is still undetermined. In view better clarifying role carbonate phase in these materials, we studied dominant Li-related diffusion carriers and their pathways on (001) surface by density functional theory (DFT) calculations, based hybrid PBE0 exchange correlation terms. four...

Two acetate ionic liquids (ILs) based on N-methyl-pyrrolidinium cation with etheric (mPEGn-) and aliphatic (butyl-) substitutions were synthetized. Electrochemical potential windows (EPWs) measured a glassy carbon electrode. The results revealed that introduction of group in the IL structure constricts EPW if compared substitution. binary mixtures ILs water characterized by Raman, Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopies Molecular Dynamics (MD)...

The segmental (bond) rotational dynamics in a polymer melt of unentangled, linear bead-spring chains is studied by molecular simulations. To single out the connectivity effects, states with limited deviations from Gaussian behavior displacement are considered. Both self and cross bond-bond correlations rank [script-l]=1,2 detail. For [script-l]=1 correlation functions precisely described expressions involving chain modes. Several approximations concerning both self- cross-correlations...

Abstract Light‐responsive shape‐changing polymers are photonastic materials: they can convert light into mechanical energy through macroscopic transformations. Indeed, photochromic molecules embedded in these polymer films present light‐induced structural modifications that trigger a significant deformation. In this theoretical study based on molecular dynamics simulations, analysis tools ranging from atomic to supramolecular scales developed investigate phenomenon. To purpose, model system...