Dynamical strengthening of covalent and non-covalent molecular interactions by nuclear quantum effects at finite temperature

Nuclear quantum effects (NQE) tend to generate delocalized molecular dynamics due to the inclusion of the zero point energy and its coupling with the anharmonicities in interatomic interactions. Here, we present evidence that NQE often enhance electronic interactions and, in turn, can result in dynamical molecular stabilization at finite temperature. The underlying physical mechanism promoted by NQE depends on the particular interaction under consideration. First, the effective reduction of interatomic distances between functional groups within a molecule can enhance the n → π* interaction by increasing the overlap between molecular orbitals or by strengthening electrostatic interactions between neighboring charge densities. Second, NQE can localize methyl rotors by temporarily changing molecular bond orders and leading to the emergence of localized transient rotor states. Third, for noncovalent van der Waals interactions the strengthening comes from the increase of the polarizability given the expanded average interatomic distances induced by NQE. The implications of these boosted interactions include counterintuitive hydroxyl–hydroxyl bonding, hindered methyl rotor dynamics, and molecular stiffening which generates smoother free-energy surfaces. Our findings yield new insights into the versatile role of nuclear quantum fluctuations in molecules and materials.

Quantum computing simulation of the hydrogen molecular ground-state energies with limited resources

In this article, the hydrogen molecular ground-state energies using our algorithm based on quantum variational principle are calculated. They are calculated through a simulator since the system of the present study (i.e., the hydrogen molecule) is relatively small and hence the ground-state energies for this molecule are efficiently classically simulable using a simulator. Complete details of this algorithm are elucidated. For this, a full description on the fermions–qubits and the molecular Hamiltonian–qubit Hamiltonian transformations, is given. The authors search for qubit system parameters ( θ 0 {\theta }_{0} and θ 1 {\theta }_{1} ) that yield the minimum energies for the system and also study the ground state energies as a function of the molecular bond length. Proposed circuit is humble and does not include many parameters compared with that of Kandala et al., the authors control only two parameters ( θ 0 {\theta }_{0} and θ 1 {\theta }_{1} ).

From atoms to bonds, angles and torsions: molecular metrics from crystal space, and two Excel implementations

Values of molecular bond lengths, bond angles and (less frequently) bond torsion angles are readily available from databases, from crystallographic software, and/or from interactive molecular and crystal visualization programs such as Jmol. However, the methods used to calculate these values are less well known. In this paper, the computational methods are described in detail, and live Excel implementations, which permit readers to readily perform the calculations for their own molecular systems, are provided. The methods described apply to both fractional coordinates in crystal space and Cartesian coordinates in Euclidean space (space in which the geometric postulates of Euclid are valid) and are vector/matrix based. In their simplest computational form, they are applied as algebraic expansions which are summed. They are also available in matrix formulations, which are readily manipulated and calculated using the matrix functions of Excel. In particular, their general formulation as metric matrices is introduced. The methods in use are illustrated by a detailed example of the calculations. This contribution provides a significant practical application which can also act as motivation for the study of matrix mathematics with respect to its many uses in chemistry.

Self-Healing Mechanisms for 3D-Printed Polymeric Structures: From Lab to Reality

Existing self-healing mechanisms are still very far from full-scale implementation, and most published work has only demonstrated damage cure at the laboratory level. Their rheological nature makes the mechanisms for damage cure difficult to implement, as the component or structure is expected to continue performing its function. In most cases, a molecular bond level chemical reaction is required for complete healing with external stimulations such as heating, light and temperature change. Such requirements of external stimulations and reactions make the existing self-healing mechanism almost impossible to implement in 3D printed products, particularly in critical applications. In this paper, a conceptual description of the self-healing phenomenon in polymeric structures is provided. This is followed by how the concept of self-healing is motivated by the observation of nature. Next, the requirements of self-healing in modern polymeric structures and components are described. The existing self-healing mechanisms for 3D printed polymeric structures are also detailed, with a special emphasis on their working principles and advantages of the self-healing mechanism. A critical discussion on the challenges and limitations in the existing working principles is provided at the end. A novel self-healing idea is also proposed. Its ability to address current challenges is assessed in the conclusions.

The Immobilization Effect of Natural Mineral Materials on Cr(VI) Remediation in Water and Soil

The effects of sepiolite, montmorillonite, and attapulgite on the removal and immobilization of Cr(VI) in water and soil were studied. X-ray diffraction (XRD) characterizations showed that the purities of these three mineral materials decreased in the following order: montmorillonite > attapulgite > sepiolite, and that their surface molecular bond types were similar. The adsorption potential of Cr(VI) in aqueous solutions of the three mineral materials was in the following order: sepiolite > attapulgite > montmorillonite. The adsorption mechanism for attapulgite was consistent with the Freundlich isotherm adsorption model, whereas that for montmorillonite was more consistent with the Langmuir model. Sepiolite had a good fitting effect for both isothermal adsorption models. For montmorillonite and attapulgite, a lower pH corresponded to a higher removal of Cr(VI). For sepiolite, however, the removal efficiency of Cr(VI) from an aqueous solution was the lowest at a pH of approximately 5.0. The results of the soil toxicity characteristic leaching procedure showed that, following the addition of 15% sepiolite, attapulgite, or montmorillonite to the contaminated soil, Cr(VI) concentrations in the leachates decreased by 16.8%, 18.9%, and 15.9%, respectively, and the total Cr concentrations in the leachates were reduced by 21.2%, 29.2%, and 17.6%. Of the three mineral materials, attapulgite demonstrated the highest Cr(VI) immobilization efficiency in soil. This study emphasizes the effect of attapulgite on the immobilization of Cr(VI) in soil and aqueous solutions, thus providing a theoretical basis for the potential application of natural mineral material remediation of Cr(VI)-contaminated aqueous solutions and soils.

Preparation and Structural Characterization of Ni3V2O8 Nanoparticles for Supercapacitor Applications

Energy perception and Energy consumption are major consideration in daytoday life in every place in world. Electrochemical energy storage devices are best remedies to fullfil the energy consumption and also serve as a alternate energy source of renewable energy devices. Here, Ni3V2O8 is developed by hydrothermal process. The crystalline phase, sixe and structural properties are identified using X- ray Diffraction techniques. The functional group and molecular bond formations are analysed using Fourier transform Infrared spectroscopy. The prepared Ni3V2O8 nanoparticles are most applied for electrode of supercapacitor applications.