Small Orbital Overlap Research Articles

Vacancy-induced heterogeneity for regulating thermoelectrics in n-type PbTe

The fact that the thermoelectric performance is far inferior to that of p-type PbTe has inspired many strategies to develop n-type PbTe thermoelectrics. Alloying PbS in n-type PbTe effectively changes the shape of a valley to trigger a heavier conduction band for improving the Seebeck coefficient, while the resulting small orbital overlap inevitably leads to phase separation hindering electron transport. The effect of vacancies on the solubility of sulfur in n-type PbTe is ambiguous; especially, the heterostructure due to phase separation in high-content PbS-alloyed PbTe also requires sufficient modification to optimize the electroacoustic transport. This motivates the current work on the introduction of vacancies by charge-balancing doping via Sb2Te3 and discovers striking new insight that the introduced vacancies can induce a new heterostructure of Pb2Sb2S5 and suppress the aggregation of Sb and PbS in high-solubility n-type PbTe–PbS. The modification of the band structure and optimization of the electron transport give rise to a prominent enhancement in electronic performance. Furthermore, the Debye–Callaway model validates the dramatic contribution of vacancy aggregation and heterostructures to lattice thermal conductivity. As a result, the synergistic modulation of electroacoustic characteristics achieves a significant improvement in both the maximum zT and the near-room-temperature zT. Understanding such unique findings is critical for applicability to other thermoelectric materials.

Long Carbon-Carbon Bonding beyond 2 Å in Tris(9-fluorenylidene)methane.

We report on our investigation of C-C bonding longer than 2.0 Å, which can be realized by perpendicularly facing two fluorenyl rings in the title compound. A small orbital overlap between the distantly positioned carbon atoms is observed as a small concentration of electrons on the X-ray electron density map. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the compound originate from the in-phase and out-of-phase interactions of the overlapping orbitals, respectively, with a gap of 2.39 eV. Solid-state 13C NMR spectroscopy shows a sharp peak at 82.9 ppm for the long-bonded carbons, and a CASSCF(6,6) calculation indicates small diradical character. The experimental and theoretical analyses reveal sufficient covalent-bonding interaction in the long-bonded carbon pair.

Control of Molecular Orientation in Organic Semiconductors Using Weak Iodine-Iodine Interactions.

Controlling the molecular orientation of materials is a key issue for improving the performance of organic semiconductor devices. Herein, we demonstrate the structure-property relationships of iodinated and noniodinated molecules based on an asymmetric thienoacene framework. The noniodinated molecule formed an antiparallel slip-stack structure with small orbital overlap between molecules. In contrast, the iodinated molecule formed a head-to-head layered-herringbone structure, and as a result, the transfer integrals became larger and the hole mobility increased significantly compared with the noniodinated material. The iodinated molecule was made into a stable and solution-processable p-type organic semiconductor with a mobility of 2.2 cm2 V-1 s-1, which was 2 orders of magnitude higher than that of the noniodinated molecule. This study reveals that controlling molecular orientations using iodine-iodine interactions is a promising strategy for accelerating the development of organic semiconductor materials.

Extending the Marcus μ-Scale of Solvent Softness Using Conceptual Density Functional Theory and the Orbital Overlap Distance: Method and Application to Ionic Liquids

The chemical hardness of a solvent can play a decisive role in solubility and reactivity in solution. Several empirical scales quantifying solvent softness have been proposed. We explore whether computed properties of solvent molecules can reproduce these experimental scales. Our “orbital overlap distance” quantifying the size of orbitals at a molecule’s surface effectively reproduces the Marcus μ-scale of solvent softness. The orbital overlap distance predicts that the surface of chemically hard solvent molecules is dominated by compact orbitals possessing a small orbital overlap distance. In contrast, the surface of chemically soft solvent molecules has a larger contribution from diffuse orbitals and a larger orbital overlap distance. Other conceptual density functional theory descriptors, including the global hardness and electronegativity, can also reproduce the Marcus scale. We further introduce a “solvent versatility” RMSD Dsurf scale quantifying variations in the surface orbital overlap distance. “Good” solvents such as DMSO, which combine chemically “hard” and “soft” sites within a single molecule, possess a large RMSD Dsurf. We conclude by applying this approach to predict the Marcus μ-parameters for widely-used ionic liquids and ionic liquid–cosolvent systems.

Suppressed Triplet Exciton Diffusion Due to Small Orbital Overlap as a Key Design Factor for Ultralong-Lived Room-Temperature Phosphorescence in Molecular Crystals.

Persistent room-temperature phosphorescence (RTP) under ambient conditions is attracting attention due to its strong potential for applications in bioimaging, sensing, or optical recording. Molecular packing leading to a rigid crystalline structure that minimizes nonradiative pathways from triplet state is often investigated for efficient RTP. However, for complex conjugated systems a key strategy to suppress the nonradiative deactivation is not found yet. Here, the origin of small rates of a nonradiative decay process from triplet states of conjugated molecular crystals showing RTP is reported. Optical microscopy analysis showed that, despite a favorable molecular stacking, an aromatic crystal with strong RTP is characterized by small diffusion length and small values of the diffusion coefficient of triplet excitons. Quantum chemical calculations reveal a large overlap between the lowest unoccupied molecular orbitals but very small overlap between the highest occupied molecular orbitals (HOMOs). Inefficient electron exchange caused by the small overlap of HOMOs prevents triplet excitons from diffusing over long distances and consequently from quenching at defect sites inside the crystal or at the crystal surface. These results will allow design of comprehensive molecular structures to obtain molecular solids with more efficient RTP.

Computational predictions of electronic properties of graphene with defects, adsorbed transition metal-oxides and water using density functional theory

The interfacial interactions between transition metal oxides (vanadium oxide VO2, vanadium pentoxide V2O5, cobalt oxide CoO and Co3O4, manganese oxide MnO2) and water adsorbates on graphene supports as solvated interfaces and influence of defects in graphene are studied using periodic density functional theory (DFT) calculations in view of their significance for applied electrochemistry. DFT complemented and synergized our experimental work. The optimized metal oxide adatom-graphene geometries identified the preferred adatom sites, whereas metal oxide-graphene strengths are correlated with the adatom distance from the graphene plane, the Metal-C overlap populations, and the adsorption energies. The presence of finite electronic density of states (DOS) near Fermi level and charge transfers between the adatom top layer and graphene supports reflect primarily covalent bonding nature. The presence of small orbital overlap integral of bonds between the s and p (and d) orbitals of the nearest carbon (graphene), carbon oxide (graphene oxide) and metal oxide atoms reveal localized orbital re-hybridization resulting in changes in DOS yielding high electrochemical activity. Moreover, for increased adatom coverage the extent of charge transfer reverses resulting in limited electroactivity. In fact, DFT calculations are corroborated with experimental findings, where graphene-based supports decorated with optimal mass loaded nanostructured Co3O4 and MnO2 (as well as V2O5) were capable of delivering maximum specific energy storage capacity (Cs) > 550 F·g−1 (Gupta et al. J. Mater. Res. 32, 301 (2017)) in contrast to higher or lower loading. The presence of defects in graphene materials results in new electronic states to endow unique functionalities that is not otherwise possible in the bulk and with adsorbed water molecules besides optimum C/O ratio in graphene oxide nanosheets that show redshift thus a decreasing bandgap and finite charge transfer from graphene to water molecules. The case examples studied in this work represent a first glimpse of what may become routine and integral step in materials design and discovery for alternative energy and sustainable environmental technologies.

Density functional theory calculations on alkali and the alkaline Ca atoms adsorbed on graphene monolayers

The adsorption of the alkali Li, K, and Na and the alkaline Ca on graphene is studied using periodic density functional theory (DFT) under various adatom coverages. The charge transfers between the adatom and the graphene sheet and the almost unchanged densities-of-states spectra in the energy region near and below the Fermi level support an ionic bond pattern between the adatom and the graphene atoms. However, the presence of small orbital overlap between the metal and the nearest graphene atom is indicative of small covalent bonding. Van der Waals interactions are examined through a semiempirical correction in the DFT functional and by comparing adatom-graphene calculations between 3% and 1.4% adatom coverages. Optimized adatom-graphene geometries identify the preferred adatom sites, whereas the adatom-graphene strength is correlated with the adsorption energy and the adatom distance from the graphene plane. Calculated electronic properties and structural parameters are obtained using hybrid functionals and a generalized gradient approximation functional paired with basis sets of various sizes. We found that due to long range electrostatic forces between the alkali/alkaline adatoms and the graphene monolayer, the adatom-graphene structural and electronic properties could be well-described by specific DFT functionals paired with high-quality adatom basis sets. For Li, K, and Na adsorbed on graphene, increased adatom surface coverage weakens the adatom-graphene interaction. However, this statement does not apply for Ca adsorbed on graphene. In this case, the Ca adsorption strength, which is stronger at higher coverages, is opposite to increases in the Ca–4s orbital population.

Observation of Ferromagnetic Exchange, Spin Crossover, Reductively Induced Oxidation, and Field-Induced Slow Magnetic Relaxation in Monomeric Cobalt Nitroxides

The reaction of [Co(II)(NO3)2]·6H2O with the nitroxide radical, 4-dimethyl-2,2-di(2-pyridyl) oxazolidine-N-oxide (L(•)), produces the mononuclear transition-metal complex [Co(II)(L(•))2](NO3)2 (1), which has been investigated using temperature-dependent magnetic susceptibility, electron paramagnetic resonance (EPR) spectroscopy, electrochemistry, density functional theory (DFT) calculations, and variable-temperature X-ray structure analysis. Magnetic susceptibility measurements and X-ray diffraction (XRD) analysis reveal a central low-spin octahedral Co(2+) ion with both ligands in the neutral radical form (L(•)) forming a linear L(•)···Co(II)···L(•) arrangement. This shows a host of interesting magnetic properties including strong cobalt-radical and radical-radical intramolecular ferromagnetic interactions stabilizing a S = (3)/2 ground state, a thermally induced spin crossover transition above 200 K and field-induced slow magnetic relaxation. This is supported by variable-temperature EPR spectra, which suggest that 1 has a positive D value and nonzero E values, suggesting the possibility of a field-induced transverse anisotropy barrier. DFT calculations support the parallel alignment of the two radical π*NO orbitals with a small orbital overlap leading to radical-radical ferromagnetic interactions while the cobalt-radical interaction is computed to be strong and ferromagnetic. In the high-spin (HS) case, the DFT calculations predict a weak antiferromagnetic cobalt-radical interaction, whereas the radical-radical interaction is computed to be large and ferromagnetic. The monocationic complex [Co(III)(L(-))2](BPh4) (2) is formed by a rare, reductively induced oxidation of the Co center and has been fully characterized by X-ray structure analysis and magnetic measurements revealing a diamagnetic ground state. Electrochemical studies on 1 and 2 revealed common Co-redox intermediates and the proposed mechanism is compared and contrasted with that of the Fe analogues.

Electronic properties of metal doped fullerides

Metal doped C 60 compounds comprise a class of materials, which includes insulators, conductors and superconductors which exhibit record superconducting transition temperatures T c for a molecularly based solid. The moderately high values of T c originate from the interaction of the conduction electrons with high frequency intramolecular phonons, and from the high density of states at the Fermi level. The high density of states and narrow band width arise from the small orbital overlap between the C 60 molecules. Hence, both electron-phonon and electron-electron interactions are expected to be important features of the of the electronic structure of metal doped fullerides. Whereas superconductivity is mediated by electron-phonon interactions in the A 3C 60 phases, we show that electron-electron interactions determine the low temperature transport properties. We compare the electronic properties of these materials with other classes of superconductors.

Collisional polarizabilities of the inert gases

We extend our previous work on collisional pair polarizabilities by including overlap effects through second order and by explicitly computing the contributions from exchange and correlation in the region of small orbital overlap. We apply the theory to the calculation of pair polarizabilities (both the anisotropy and the trace) of inert gas diatoms. The agreement with coupled Hartree-Fock calculations and experimental optical properties is good, and suggests that this simple method should provide a feasible approach for similar descriptions of molecular gases.

On the exchange repulsion between beryllium atoms

Assuming the wave functions for free atoms in the form of the closed-shell SCF determinants, the first-order interaction energy for a system of three ground-state beryllium atoms has been computed. The decomposition of two and three-body interaction energies into individual, intershell contributions has been proposed. The results show that only the electrostatic energy is well approximated by the interaction of outer shells. For the two and three-body exchange energies this approximation is reliable only in the region of small orbital overlap. It has also been found that the three-body contribution to the interaction energy is considerably greater than in the case of the interaction of helium atoms.

H-H-interactions in the region of small orbital overlap

Calculations have been made on the lowest state of H2 in the region 4–6 a.u. with a view to elucidating some of the problems arising in the perturbation theory of intermolecular forces in the region of small orbital overlap. The conclusions are that a small basis set of non-orthogonal functions, which in a variation calculation gives reasonably good total energies, can give a poor approximation to the second-order perturbation energies. Variational calculations using the separate basis functions appropriate to induction, dispersion and charge-transfer energies show that these energies may be reasonably added together to reproduce the variational calculations from the total basis set.

Deviations from Pairwise Additivity in Intermolecular Potentials

The various contributions to the interaction energy as defined in the theory of intermolecular forces in the region of small orbital overlap [J. N. Murrell, M. Randic, and D. R. Williams, Proc. Roy. Soc. (London) A284, 566 (1965)] are generalized to many-body systems. Each contribution is examined in a qualitative manner for deviations from pairwise additivity. Numerical calculations of the exchange energy for three helium atoms in triangular and linear arrays are made utilizing the available expansions of Slater-type orbitals in terms of a Gaussian set. The nonadditive terms for these energies are then calculated over a range of interacting distances. It is concluded that for weakly interacting nonpolar molecules nonpairwise additive terms in the intermolecular potential are likely to be small.

Intermolecular Forces in the Region of Small Orbital Overlap

The perturbation method of Yaris for the case where the unperturbed wavefunction is not an eigenfunction of the unperturbed Hamiltonian is developed to give an expression for intermolecular energies in the region of small orbital overlap. The resulting expressions are the same as these obtained earlier using a more traditional aproach, but the derivation does not suffer the lack or rigor in this earlier treatment.

The theory of intermolecular forces in the region of small orbital overlap

A general theory is given of the intermolecular energy when there is small overlap between orbitals of different molecules. The energy is expanded as a power series in the intermolecular potential U and the overlap integral S , and expressions are given for the contributions to the energy up to order U 2 S 2 . We have defined exchange energy by the contribution of order U S 2 . This leads to a simpler expression than the more familiar valence-bond definition of the term. The energy contributions of order U 2 S 2 may be subdivided into two parts, exchange polarization energy and charge transfer energy. The mathematical validity of this subdivision is discussed.