A5031384734- Metal-Organic Frameworks: Synthesis and Applications
- Advanced Chemical Physics Studies
- Inorganic Fluorides and Related Compounds
- X-ray Diffraction in Crystallography
- Zeolite Catalysis and Synthesis
- Crystallography and molecular interactions
- Crystal Structures and Properties
- Machine Learning in Materials Science
- Boron and Carbon Nanomaterials Research
- Solid-state spectroscopy and crystallography
- Magnetism in coordination complexes
- High-pressure geophysics and materials
- Spectroscopy and Quantum Chemical Studies
- Hydrogen Storage and Materials
- Glass properties and applications
- Nonlinear Optical Materials Research
- Chemical Synthesis and Characterization
- Clay minerals and soil interactions
- Catalysis and Oxidation Reactions
- Mesoporous Materials and Catalysis
- Catalytic Processes in Materials Science
- Gas Sensing Nanomaterials and Sensors
- Superconductivity in MgB2 and Alloys
- Thermal Expansion and Ionic Conductivity
- Thermal and Kinetic Analysis
University of Turin
2016-2025
National Interuniversity Consortium of Materials Science and Technology
2012-2024
Torino e-district
2015-2020
Interface (United States)
2015-2020
Li Creative Technologies (United States)
2015
Hacettepe University
2010
Universitat de les Illes Balears
2000-2010
National Research Council
2007-2009
Institute of Polymers, Composites and Biomaterials
2007-2009
University of Modena and Reggio Emilia
2008
Through a combined use of experimental and theoretical approaches such as XRPD, EXAFS, IR, UV−vis spectroscopies ab initio periodic DFT calculations, we report detailed characterization structural, vibrational, electronic properties UiO-66 (Zr-BDC MOF) in its hydroxylated dehydroxylated forms. The stability the materials with respect to most common solvents, acids, bases is determined by combining XRPD TGA/MS techniques. structures two forms are refined through an interactive XRPD/EXAFS...
The latest release of the Crystal program for solid‐state quantum‐mechanical ab initio simulations is presented. adopts atom‐centered Gaussian‐type functions as a basis set, which makes it possible to perform all‐electron well pseudopotential calculations. Systems any periodicity can be treated at same level accuracy (from 0D molecules, clusters and nanocrystals, 1D polymers, helices, nanorods, nanotubes, 2D monolayers slab models surfaces, actual 3D bulk crystals), without artificial...
The capabilities of the C rystal14 program are presented, and improvements made with respect to previous rystal09 version discussed. is an ab initio code that uses a Gaussian‐type basis set: both pseudopotential all‐electron strategies permitted; latter not much more expensive than former up first‐second transition metal rows periodic table. A variety density functionals available, including as extreme case Hartree–Fock; hybrids various nature (global, range‐separated, double) can be used....
Abstract CRYSTAL [1] computes the electronic structure and properties of periodic systems (crystals, surfaces, polymers) within Hartree-Fock [2], Density Functional various hybrid approximations. was developed during nearly 30 years (since 1976) [3] by researchers Theoretical Chemistry Group in Torino (Italy), Computational Materials Science group CLRC (Daresbury, UK), with important contributions from visiting researchers, as documented main authors list bibliography. The basic features...
The problem of numerical accuracy in the calculation vibrational frequencies crystalline compounds from hessian matrix is discussed with reference to alpha-quartz (SiO(2)) as a case study and specific implementation CRYSTAL code. Hessian obtained by differentiation analytical gradient energy respect atomic positions. process calculating involves two steps: determination equilibrium geometry, themselves. parameters controlling truncation Coulomb exchange series Hartree-Fock, quality grid used...
The B3LYP method augmented with a damped empirical dispersion term (−f(R)C6/R6) is shown to yield structures and cohesive energies, for representative set of molecular crystals, in excellent agreement experimental data. Vibrational lattice modes crystalline urea are also reported be very close experiment. role the damping function scaling contribution has been analyzed as well relevance BSSE prediction structure energy.
The recently discovered UiO-66/67/68 class of isostructural metallorganic frameworks (MOFs) [J. H. Cavka et al. J. Am. Chem. Soc., 2008, 130, 13850] has attracted great interest because its remarkable stability at high temperatures, pressures and in the presence different solvents, acids bases [L. Valenzano Mater., 2011, 23, 1700]. UiO-66 is obtained by connecting Zr6O4(OH)4 inorganic cornerstones with 1,4-benzene-dicarboxylate (BDC) as linker resulting a cubic MOF, which already been...
Adsorption of carbon monoxide, dinitrogen, and dioxide on the porous metal−organic framework Mg-MOF-74 was investigated by means a combined methodology comprising variable-temperature infrared spectroscopy ab initio periodic DFT-D calculations using CRYSTAL code. Both CO N2 were found to form nearly linear (Mg2+···CO Mg2+···NN) adsorption complexes, in contrast with CO2, which forms an angular Mg2+···OCO complex. From IR spectra recorded at variable-temperature, standard enthalpy (ΔH0) be...
Using Brillouin scattering, we measured the single-crystal elastic constants (C(ij)'s) of a prototypical metal-organic framework (MOF): zeolitic imidazolate (ZIF)-8 [Zn(2-methylimidazolate)(2)], which adopts sodalite topology and exhibits large porosity. Its C(ij)'s under ambient conditions are (in GPa) C(11)=9.522(7), C(12)=6.865(14), C(44)=0.967(4). Tensorial analysis reveals complete picture anisotropic elasticity in cubic ZIF-8. We show that ZIF-8 has remarkably low shear modulus G(min)...
We present an unambiguous identification of low-frequency terahertz vibrations in the archetypal imidazole-based metal-organic framework (MOF) materials: ZIF-4, ZIF-7, and ZIF-8, all which adopt a zeolite-like nanoporous structure. Using inelastic neutron scattering synchrotron radiation far-infrared absorption spectroscopy, conjunction with density functional theory (DFT), we have pinpointed major sources vibrational modes. Ab initio DFT calculations revealed complex nature collective THz...
The identification and quantification of defects are undoubtedly thorough challenges in the characterization "defect-engineered" metal–organic frameworks (MOFs). UiO-66, known for its exceptional stability defect tolerance, has been a popular target defect-engineering studies. Herein, we show that synthesizing UiO-66 presence an excess benzoic acid is reliable method obtaining samples with very high concentration missing-cluster defects, allowing one to modulate specific properties (i.e.,...
CRYSTAL is a periodic ab initio code that uses Gaussian-type basis set to express crystalline orbitals (i.e., Bloch functions). The use of atom-centered functions allows treating 3D (crystals), 2D (slabs), 1D (polymers), and 0D (molecules) systems on the same grounds. In turn, all-electron calculations are inherently permitted along with pseudopotential strategies. A variety density functionals implemented, including global range-separated hybrids various natures and, as an extreme case,...
The spontaneous polarization and the piezoelectric constants of ZnO BeO are calculated at an ab initio quantum-mechanical level by using two alternative strategies, namely, through Berry phase scheme applied to delocalized crystalline orbitals, definition well-localized Wannier functions. sets results, obtained in same computational conditions (both schemes implemented CRYSTAL code) compare extremely well, good agreement with available experimental data.
MOF-5 is by far the most relevant member of new class metal–organic framework materials and has been adopted as a case study to show that reliable ab initio prediction properties complex systems can be obtained means solid state computational tool like CRYSTAL code. Structure, electronic vibrational frequencies computed at B3LYP level theory are reported discussed. Animations representing vibrations available web site: http://www.crystal.unito.it/vibs/mof5
A comparative analysis of the intermolecular energy for a data set including 60 molecular crystals with large variety functional groups has been carried out using three different computational approaches: (i) method based on physically meaningful empirical partition interaction (PIXEL), (ii) density methods posteriori correction dispersion interactions (DFT-D), and (iii) full periodic ab initio quantum mechanical Møller-Plesset perturbation theory electron correlation localized crystal...
Structural and vibrational features of hexagonal hydroxyapatite HA [Ca10(PO4)6(OH)2, space group P63] are computed ab initio within a periodic approach using the CRYSTAL03 program B3LYP hybrid functional with Gaussian-type basis set polarized double zeta quality. Experimental lattice parameters internal coordinates have been fully optimized final structure characterized by means its band structure, density states Mulliken analysis. The full harmonic spectrum at Γ point has also compares well...
Breathtaking MOFs: DFT calculations reveal that the exceptional, thermally induced density change of metal–organic framework MIL53(Al) is controlled by a competition between short- and long-range interactions entropic factors. As shown in picture (C green, Al cyan, O red, H white), dispersive phenyl rings are responsible for stabilizing narrow-pore form at low temperature. At 325–375 K, vibrational entropy causes structure to expand markedly, permitting large volumes light gases be adsorbed....
We extend the previously developed geometrical correction for inter- and intramolecular basis set superposition error (gCP) to periodic density functional theory (DFT) calculations. report gCP results compared those from standard Boys-Bernardi counterpoise scheme large The applicability of method molecular crystals as main target is tested benchmark X23. It consists 23 noncovalently bound introduced by Johnson et al. (J. Chem. Phys. 2012, 137, 054103) refined Tkatchenko 2013, 139, 024705)....
Density functional theory is applied with a hybrid to which parametrized damped 1/r6 term has been added account for dispersion (B3LYP+D*). This method used periodic boundary conditions get the structures of adsorption complexes. Dispersion substantial share on calculated energies (46–77%). For these structures, are also high-level (MP2 complete basis set extrapolation):low level (B3LYP+D*) method. The MP2 calculations performed cluster models. Comparison made experimental heats adsorption....
We use density functional theory to reveal the detailed elastic properties of two topical ZIF materials comprising same chemical composition but different crystalline structures. ZIF-4 was found exhibit a negative Poisson's ratio, representing first ‘auxetic-ZIF’ be identified.
We employed a combination of theoretical and experimental techniques to study the metal–organic framework (MOF)-mechanics central paddle-wheel Cu<sub>3</sub>(BTC)<sub>2</sub> porous structure, commonly designated as HKUST-1.