Molecular and electronic structure of δ-valerothiolactone

The crystal structure of the six-member heterocyclic δ-valerothiolactone (1-thiocycloalkan-2-one) compound has been determined by X-ray diffraction at low temperature, revealing that its skeleton adopts a half-chair conformation. The conformation around the thioester group is almost planar with an anti orientation of the C=O double bond with respect the S-C single bond [C(2)-S(1)-C(6)-O(1) = 176.26(8)°]. The skeletal parameters, especially valence angles [∠C5-C6-S = 121.19(6)°, ∠O=C6-C5 = 122.25(8)°, ∠C6-S-C2 = 106.80(4)°], differ from those typically found in acyclic thioester compounds, symptomatic of the presence of strain effects. The conventional ring strain energy was determined to be 7.5 kcal/mol at the MP2/6-311++G(d,p) level of calculation within the hyperhomodesmotic model approximation. Moreover, the valence electronic structure was investigated by HeI photoelectron spectroscopy assisted by quantum chemical calculations at the OVGF/6-311++G(d,p) level of theory. The first three bands at 9.35, 9.50, and 11.53 eV denote ionizations related with the n(S), n(O), and π(C=O) orbitals, respectively, demonstrating the importance of the -SC(O)- group in the outermost electronic properties.     

Iron–sulfur clusters and their electronic and magnetic properties

Iron–sulfur clusters of diverse nuclearities constitute the active sites of a large and prominent family of metalloproteins which play essential roles in all living organisms, such as in electron transfer chains, reduction catalysis, photosynthesis, the respiratory chain and nitrogen fixation. This review is devoted to the presentation of the current state of understanding of their electronic and magnetic properties, which is here derived from their Mössbauer, EPR and ENDOR spectroscopic properties. These techniques constitute fine tools for characterization and provide knowledge of the different oxidation states of these proteins, although our interest here will be mainly centered on the [4Fe–4S*]ⁿ⁺ clusters (with n=1–3). A qualitative physical model involving the competing magnetic interactions in these clusters is discussed. Moreover, this article contains new developments on two more specialized subjects:

• 1.some quantitative consequences of an already published theory of the g-tensors of [4Fe–4S*]ⁿ⁺ clusters (n=1,3) will be derived in Section 3;
• 2.a model permitting the rationalization, from very simple ingredients and formulae, of the redox potentials of a whole set of known synthetic redox clusters (with 1, 2, 3, 4 and 6 iron atoms) will be presented in the final Section 6.

     

Magnetic and electronic properties of α-graphyne nanoribbons

Based on the first-principles calculations, we investigate the magnetic and electronic properties of α-graphyne nanoribbons (NRs). We show that all the armchair α-graphyne NRs are nonmagnetic semiconductors with band gaps as a function of ribbon widths. The zigzag α-graphyne NRs are found to have magnetic semiconducting ground state with ferromagnetic ordering at each edge and opposite spin orientation between the two edges. Under the application of transverse electric field, we further predict the existence of half-metallicity in the zigzag NRs which strongly depends on the width of the ribbon.     

MXene fibers for electronic textiles: Progress and perspectives

The rapid evolution of portable and wearable electronic devices has fueled the development of smart functional textiles that are able to conduct electricity, sense body movements, or store energy. One main challenge inhibiting the further development of functional textile-based electronics is the lack of robust functional fibers with suitable electrical, electrochemical and sensing functionalities. MXenes, an emerging family of two-dimensional(2D) materials, have shown to be promising candidates...     

Laser ionization spectra and electronic structure of Kn and NaKn−1 clusters

Photoionization of small K_n and NaK_n−1 clusters with n ⩽ 34 has been achieved in a crossed laser-molecular-beam experiment. The relative ion peak intensities in mass spectra reveal fragmentation effects which are wavelength-dependent. The vertical ionization profiles in the threshold region give some insight into the electronic structure.     

The relationship between electronic charges and lengths of σ-bonds

Summary A dependence was shown to exist between the electronic charges and the lengths of -bonds of a saturated carbon atom, which permitted us to explain and to correct the existing data on interatomic distances.     

Acid–base behavior of oxides and their electronic structure

We attempted to simplify and unify the former concepts describing the acid base character of oxides on the basis of their band structure. Duffy optical basicity, Smith acid scale and Bratsch electronegativity model can simply be linked by taking into account the electronegativity and the chemical hardness of the oxides: an acidic oxide has a strong electronegativity together with a strong chemical hardness while a basic oxide has a low electronegativity associated with a weak chemical hardness.     

Glass-like electronic and thermal transport in crystalline cubic germanium selenide

Thermoelectric properties of orthorhombic or rhombohedral GeSe have attracted great attention recently,with the rise of its structural analog Sn Se.However,the p-type cubic GeSe with higher symmetry and higher valence band degeneracy,which might exhibit higher thermoelectric performance,has never been synthesized.Here we report on the successful synthesis of p-type crystalline cubic GeSe by alloying with Sb2Te3 and the spontaneously formed Ge-vacancies.An unexpected glass-like temperature independent lattice thermal conductivity is observed in crystalline cubic GeSe,which results from strong phonon scattering by vacancy-induced disorders.Combining the multiple scattering theory and chemical bond analysis,we further reveal the existence of Anderson localization induced by Ge-vacancies.The Anderson localization results in a nearly constant Seebeck coefficient with increasing the carrier concentration.These results provide a general insight towards understanding and improving the thermoelectric properties of thermoelectric materials with vacancies and atomic-scale disorders.     

Dicyano and pyridine derivatives of β-carotene: synthesis and vibronic, electronic, and photophysical properties

Density functional theory and time-dependent density functional theory calculations provide pictures of the molecular orbitals involved in the ground and excited states of two cyano derivatives of 8'-apo-β-caroten-8'-al synthesized via an acid-base-catalyzed Knoevenagel condensation reaction. Population analysis shows that the symmetry-allowed transition, S(0) ((1)A(g)) → S(2) ((1)B(u)) based on the C(2h) symmetry is a HOMO (highest occupied molecular orbital) to LUMO (lowest unoccupied molecular orbital) π → π* transition with electron densities located mostly on the polyene chain. Calculated and actual steady-state absorption spectra show similar features with low-energy peak maxima between 550 and 600 nm.     

Geometry optimization and electronic structures of molecules H_3AXAH_3

The geometries of molecules H_3AXAH_3(X=O,S,Se and A=C,Si)have been optimizedusing STO-3G ab initio calculations and gradient method and the results are in good agreement withreported experimental values.From the STO-3G optimized geometries,we have also calculated theelectronic structures of these molecules using 4-31G and 6-31G basis sets to obtain the MO energies.atomic net charges and dipole moments.The ionization potentials calculated by 6-31G basis set are ingood agreement with experimental values.     

Möbius and twisted graphene nanoribbons: stability, geometry, and electronic properties

Results of classical force field geometry optimizations for twisted graphene nanoribbons with a number of twists N(t) varying from 0 to 7 (the case N(t)=1 corresponds to a half-twist M?bius nanoribbon) are presented in this work. Their structural stability was investigated using the Brenner reactive force field. The best classical molecular geometries were used as input for semiempirical calculations, from which the electronic properties (energy levels, HOMO, LUMO orbitals) were computed for each structure. CI wavefunctions were also calculated in the complete active space framework taking into account eigenstates from HOMO-4 to LUMO+4, as well as the oscillator strengths corresponding to the first optical transitions in the UV-VIS range. The lowest energy molecules were found less symmetric than initial configurations, and the HOMO-LUMO energy gaps are larger than the value found for the nanographene used to build them due to electronic localization effects created by the twisting. A high number of twists leads to a sharp increase of the HOMO-->LUMO transition energy. We suggest that some twisted nanoribbons could form crystals stabilized by dipolar interactions.     

Photoelectron spectroscopy and electronic structures of β-diketonate complexes of rare-earth elements

The electronic structures of lanthanide tris(β-diketonate) complexes and their adducts, being of interest as luminophores, were studied by UV photoelectron spectroscopy of vapors and X-ray photoelectron spectroscopy. The spectral regularities identified by the density functional theory revealed the influence of the substitution of the Me groups in the ligands by Bu^t, CF₃, and neutral ligand in the adducts on the electronic structure of the complexing agent from Pr to Lu.     

Structural and electronic properties of zinc blende BxGa1−xN nitrides

First principles total energy calculations were carried out to investigate structural and electronic properties of zinc blende GaN, BN and B_xGa_1?xN solid solutions. We have calculated lattice parameters, bulk modulus, pressure derivative and B_xGa_1?xN band gap energy for zinc blende-type crystals of the compositions x = 0, 0.25, 0.5, 0.75, 1. Discussions will be given in comparison with results obtained with other available theoretical and experimental results.     

First-principles study of the crystal and electronic structures of α-tetragonal boron

The crystal and electronic structures of α-tetragonal (α-t) boron were investigated by first-principles calculation. Application of a simple model assuming 50 atoms in the unit cell indicated that α-t boron had a metallic density of state, thus contradicting the experimental fact that it is a p-type semiconductor. The presence of an additional two interstitial boron atoms at the 4c site made α-t boron semiconductive and the most stable. The cohesive energy per atom was as high as those of α- and β-rhombohedral boron, suggesting that α-t boron is produced more easily than was previously thought. The experimentally obtained α-t boron in nanobelt form had about two interstitial atoms at the 8i sites. We consider that the shallow potential at 8i sites generates low-energy phonon modes, which increase the entropy and consequently decrease the free energy at high temperatures. Calculation of the electronic band structure showed that the highest valence band had a larger dispersion from Γ to Z than from Γ to X; this indicated a strong anisotropy in hole conduction.     

Strong π-delocalization and substitution effect on electronic properties of dithienylpyrrole-containing bipyridine ligands and corresponding ruthenium complexes

The first dithienylpyrrole (DTP)-based bipyridine ligands has been prepared and coordinated with ruthenium to give the corresponding homoleptic complexes. Bipyridine was bound at pyrrole (DTP(1)) or thiophene (DTP(2)) ring. A strong bathochromic effect was obtained by switching from pyrrole to thiophene for ligands and complexes. Interestingly the DTP(2) series offered a wide absorption window from UV to visible domain with an almost constant absorbance. These effects are due to a larger extent of delocalization as supported by DFT calculations and photophysical measurements.     

Pyrazolium- and 1,2-cyclopentadiene-based ligands as σ-donors: a theoretical study of electronic structure and bonding

A high-level theoretical investigation of 1,2-cyclopentadiene (4) was performed using density functional theory and wave function methods. The results reveal that, in contrast to earlier assumptions, the ground state of this ephemeral "allene" is carbene-like with a small diradical component. Furthermore, the electronic structure and chemistry of 4 are found to parallel that of 1,2,4,6-cycloheptatetraene: both molecules possess a low-lying excited singlet state with a closed-shell carbenic structure, enabling rich coordination chemistry. Energy decomposition analyses conducted for currently unknown metal complexes of 4 as well as those involving stable carbenes based on the pyrazolium framework (aka "bent allenes" or remote N-heterocyclic carbenes) indicate that all investigated ligands form particularly strong metal-carbon bonds. Most notably, without exocyclic π-type substituents, 4 and pyrazolin-4-ylidenes are the strongest donor ligands examined, in large part because of the energy and shape of their highest occupied molecular orbital. As a whole, the current work opens a new chapter in the chemistry of 1,2-cyclopentadiene, which is hoped to spark renewed interest among experimentalists. In addition, results from the conducted bonding analyses underline that more emphasis should be placed on purely carbocyclic carbenes as unprecedented σ-donor strengths can be realized through this route.     

Study on molecular and electronic structures, and spectroscopic properties of azide ruthenium complexes with pyridine and β-picoline ligands

The [Ru(N₃)₂(PPh₃)(py)₃] and [Ru(N₃)₂(PPh₃)₂(β-pic)₂] complexes have been prepared and studied by IR, NMR, UV-Vis spectroscopy and X-ray crystallography. The complexes were prepared in the reactions of [RuCl₂(PPh₃)₃] with pyridine, β-picoline and NaN₃ in methanol solutions. The electronic structures of the obtained complexes have been calculated using the DFT/TD-DFT method. The trans effect of triphenylphosphine on the pyridine molecule has been studied using NBO and molecular orbital terms, and impact of the acceptor properties of the halide/pseudohalide co-ligands was indicated.     

Charge transport and electronic properties of N-heteroquinones: quadruple weak hydrogen bonds and strong π–π stacking interactions

The charge transport and photophysical properties of N-heteroquinones, which can function as n-type organic semiconductors in organic field-effect transistors (OFETs) with high electron mobility, were systematically investigated using hopping model, band theory, and time-dependent density functional theory (TDDFT). The calculated absorption spectra and electron mobility are in good agreement with experimental results. To the studied compounds, subtle structural modifications can greatly reduce the reorganization energy. There are two main kinds of intermolecular interaction forces of the studied compounds in the crystal, which result from intermolecular π–π and hydrogen bonds interactions, respectively. The results of hopping model show that the electron transport properties are mainly determined by pathways containing intermolecular π–π interactions, and hole transport properties are mainly determined by pathways containing intermolecular hydrogen bonds from the standpoint of transfer integral. Moreover, electronic transfer integral value increases with the enhancement of intermolecular overlap corresponding to the overlap extent of π–π packing. Hole transfer integral value decreases with decreasing the number of hydrogen bonds. This means that charge transport properties can be efficiently tuned by controlling the relative positions of the molecules and the number of hydrogen bonds. The analysis of band structure also supports the conclusion of hopping model.     

Geometry,electronic structure,and magnetic ordering of iron–carbon nanoparticles

The geometry optimization of Fe _n C _m and Fe _n C _m ⁺ nanoparticles from FeC₄ to Fe₇C₈ was carried out using DMol³ method. The most stable isomers for neutral and charged clusters are found with the use of ‘binomial’ scheme. For each investigated composition, the value of binding energy per atom for the ground isomer was evaluated as well as the number of configurations with binding energies which are close to that of the ground geometry. In almost all compositions, the isomers with ferromagnetic ordering of spins on Fe atoms are found to have the greater dissociation energy than those with any other spin ordering.