A theoretical study of N–H ··· π H-bond interaction of pyrrole: from clusters to the liquid

The N–H?···?π H-bond interactions of clusters and liquid formed by pyrrole molecules were investigated by Quantum Mechanics (QM) and classical Molecular Dynamics (MD), respectively. Based on the optimized geometry at the B97-D/aug-cc-pVTZ level of theory including dispersion correction, the nature and the origin of N–H?···?π H-bond interactions were unveiled by atoms in molecules (AIM), natural bond orbital (NBO), and energy decomposition analysis (EDA). Among them, the AIM analysis gives evidence to the presence of N–H?···?π H-bond interactions, the NBO examination reveals that π?→?σ* donor-acceptor orbital interaction is of great importance. EDA study indicates that N–H?···?π interactions are governed by the electrostatic and dispersion term. Meanwhile, MD simulation with OPLS-AA (optimized potentials for liquid simulations all-atom) was applied to study the pure liquid pyrrole at different temperature. The results confirm the existence of the N–H?···?π H-bond in the pure liquid pyrrole, and further characterized the structures of this H-bond which is somewhat different to the clusters.     

Theoretical investigation of the backbone···π and π···π stacking interactions in substituted-benzene||3-methyl-2′-deoxyadenosine: a perspective to the DNA repair

The π-stacking effects of substituted benzenes on the N-glycosidic bond strength of 3-methyl-2'-deoxyadenosine (3-MDA) were studied by quantum mechanical calculations. Although all substituents enhance the stacking interactions, enhancement is higher for the electron-donating (ED) substituents. When the overall binding energy is separated into the π···π (ΔE_π···π) and backbone···π (ΔE_bb···π) contributions, the ED and electron-withdrawing (EW) substituents increase those contributions, respectively. Both the ED and EW substituents decrease the distance between the centres of stacked rings, while the EW ones increase the N-glycosidic bond length. The electron charge density calculated at the C--N bond critical point (ρ_C–N) is in linear correlation with the backbone···π interaction, not with the π···π interaction. This study also shows that the charge transfer from X-Ben to 3-MDA is in linear correlation with the ΔE_π···π and the change in the charge on the sugar ring is in better accordance with the backbone···π interaction. The N7 proton affinity (PA_N7), with a key role in the depurination process, is highly affected by the π···π interactions. Thus, both interactions must be considered because of the balance between the backbone···π and π···π contributions in these biomolecular systems.     

On difference of properties between organic fluorine hydrogen bond C–H···F–C and conventional hydrogen bond

The existence of C–H···F–C hydrogen bonds in the complexes of trifluoromethane and cyclic molecule (oxirane, cyclobutanone, dioxane, and pyridine) has been experimentally proven by Caminati and co-workers. This study presents a theoretical investigation on these C–H···F–C hydrogen bonds at B97D/6-311++G^** and MP2/6-311++G^** levels, in terms of C–H vibrational frequency shifts, atoms in molecules characteristics, and the bonding feature of C–H···F–C hydrogen bonds. It is found that in three important aspects, there are significant differences in properties between C–H···F–C and conventional hydrogen bonds. The C–H···F–C hydrogen bonds show a blueshift in the C–H vibrational frequencies, instead of the X–H normal redshift in X–H···Y conventional hydrogen bonds. The natural bond orbital (NBO) analyses show that σ and p types of lone pair orbitals of the F atom to an antibonding σ^*_H–C orbital form a dual C–H···F–C hydrogen bond. Such a dual hydrogen bonding leads to the proton acceptor directionality of the C–H···F–C hydrogen bond softer. Our studies also show that the Laplacian of the electron density (▽²ρ_BCP) is not always a good criterion for hydrogen bonds. Therefore, we should not recommend the use of the Laplacian of the electron density as a criterion for C–H···F–C hydrogen bonds.     

Properties of cationic pnicogen-bonded complexes F4-nHnP+:N-base with H–P···N linear and n = 1–4

Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the pnicogen-bonded complexes F_4-nH_nP⁺:N-base, for n = 1–4, each with a linear or nearly linear H_ax–P···N alignment. The sp³-hybridised nitrogen bases include NH₃, NClH₂, NFH₂, NCl₂H, NCl₃, NFCl₂, NF₂H, NF₂Cl, and NF_3, and the sp bases are NCNH₂, NCCH₃, NP, NCOH, NCCl, NCH, NCF, NCCN, and N₂. Binding energies increase as the P–N distance decreases, with an exponential curve showing this relationship when complexes with sp³ and sp hybridised bases are treated separately. However, the correlations are not as good as they are for the complexes F_4-nH_nP⁺:N-base for n = 0–3 with F–P···N linear. Different patterns are observed for the change in the binding energies of complexes with a particular base as the number of F atoms in the acid changes. Thus, the particular acid–base pair is a factor in determining the binding energies of these complexes.

Three different charge-transfer interactions stabilise these complexes, namely N_lp→σ*P–H_ax, N_lp→σ*P–F_eq, and N_lp→σ*P–H_eq. Unlike the corresponding complexes with F–P···N linear, N_lp→σ*P–H_ax is not always the dominant charge-transfer interaction, since N_lp→σ*P–F_eq is greater in some complexes. N_lp→σ*P–H_eq makes the smallest contribution to the total charge-transfer energy. The total charge-transfer energies of all complexes increase exponentially as the P–N distance decreases in a manner very similar to that observed for the series of complexes with F–P···N linear.

Equation-of-motion coupled cluster singles and doubles (EOM-CCSD) spin–spin coupling constants ^1pJ(P–N) across the pnicogen bond vary with the P–N distance, but different patterns are observed which depend on the nature of the acid, and for some acids, on the hybridisation of the nitrogen base. ^1pJ(P–N) values for complexes of F₃HP⁺ initially increase as the P–N distance decreases, reach a maximum, and then decrease with decreasing P–N distance as the P···N bond acquires increased covalent character. ^1pJ(P–N) for complexes with H–P···N linear and those with F–P···N linear exhibit similar distance dependencies depending on the number of F atoms in equatorial positions and the hybridisation of the base. Complexation may increase, decrease, or leave the P–H_ax distance unchanged, but ¹J(P–H_ax) always decreases relative to the corresponding isolated ion. Decreasing ¹J(P–H_ax) can be related to decreasing intermolecular P–N distance.     

Structural and spectroscopic investigation of the N-methylformamide–water (NMF···3H2O) complex

In this work, theoretical studies on the structure, molecular properties, hydrogen bonding, and vibrational spectra of the N-methylformamide–water (NMF···3H₂O) complex will be presented. The molecular geometry was optimised by using Hartree–Fock (HF), second Møller–Plesset (MP2), and density functional theory methods with different basis sets. The harmonic vibrational frequencies are computed by using the B3LYP method with 6-311++G(d,p) as a basis set and then scaled with a suitable scale factor to yield good coherence with the observed values. The temperature dependence of various thermodynamic functions (heat capacity, entropy, and enthalpy changes) was also studied. A detailed analysis of the nature of the hydrogen bonding, using natural bond orbital (NBO) and topological atoms in molecules theory, has been reported.     

The 8π spectrometer

The 8π spectrometer installed at the TRIUMF-ISAC radioactive beam facility provides a powerful and versatile detection system for radioactive decay, allowing measurements of γ rays and conversion electrons with high resolution, tagging on β particles, and fast-timing measurements. The facility supports a wide program of research in the fields of nuclear structure, nuclear astrophysics and fundamental symmetries with low-energy radioactive beams.     

Ionization in Ps–H scattering

Coulomb–Born approximation has been used to study three different types of ionization in positronium (Ps) and hydrogen scattering. The present Ps–H system contains four centers; we have considered all the Coulomb interactions and neglected exchange assuming the fact that at relatively higher energies above thresholds, the effect of exchange is not so important. All the important target elastic and inelastic channels are included. The non-unitarity problem in the target elastic channels, discussed by McAlinden et al. in 1996 in their positronium–atom scattering studies is overcomed in the present calculation using the orthonormality properties of target wavefunctions and a simple algebra. Comparative studies are made among ionization cross sections with different target excitations and different Ps-excitations together with summed Ps-ionization, summed H-ionization, both-ionization, summed excitation, total ionization and total cross sections. The present Letter indicates the importance of all the three different types of ionization and the importance of target elastic channels in Ps–H scattering.     

Birationality of Berglund–Hübsch–Krawitz Mirrors

We investigate a multiple mirror phenomenon arising from Berglund–Hübsch–Krawitz mirror symmetry. We prove that the different mirror Calabi–Yau orbifolds which arise in this context are in fact birational to one another.     

Effect of substitution and cooperativity on the Cl–F blue shift in single-electron halogen-bonded H3C ··· ClF complex

The effect of substitution and cooperativity on the blue shift of Cl–F stretch vibration in H₃C ··· ClF complex has been studied with quantum chemical calculations at the UMP2(Full)/aug-cc-pVTZ level. The electron-withdrawing group (F atom) in the electron donor decreases the blue shift, whereas the electron-donating group (methyl group) in the electron donor cause it to increase. The cooperativity between two different types of halogen bonds in H₃C ··· ClF ··· ClF complex enhances the strength of single-electron halogen bond and the blue shift. The natural bond orbital (NBO) and atoms in molecules (AIM) analyses have been performed for the halogen-bonded complexes.     

Molecular two-centre integrals between 2 pπ and 3 pπ atomic orbitals

The evaluation of two-centre Coulomb-penetration and exchange-penetration integrals is discussed. All possible penetration integrals between 2pπ and 3pπ atomic orbitals exponent α are reduced analytically and tabulated for α = 1·00 (0·25) 10·00.     

Four-body calculations of elastic scattering in H–H̄ collisions

We present a nonadiabatic treatment of the hydrogen-antihydrogen system. The technique used to describe H- H? collisions is based on the coupled rearrangement channels method. Within this approach the total, nonadiabatic wave function of the system is divided into two parts: an inner and an outer one. To describe the inner part a set of square-integrable 4-body functions is used. These functions are obtained by a diagonalization of the total Hamiltonian projected on a chosen L ² subspace, they explicitly contain components of various arrangement channels expressed in terms of corresponding Jacobi coordinates. The outer part of the total wave function reflects its asymptotic character. Our procedure leads to the system of non-local integro-differential equations that are solved iteratively and simultaneously determine both the shape of the outer part of the wave function and the coefficients in the four-body expansion of the inner part. Using this formalism we perform the one-channel calculation of the elastic scattering to obtain the S-matrix and nonadiabatic scattering length.     

Comprehensive study of a 4H–SiC MES–MOSFET

In this paper, we studied the enhancement of the breakdown voltage in the 4H–SiC MESFET–MOSFET (MES–MOSFET) structure which we have proposed in our previous work. We compared this structure with Conventional Bulk-MOSFET (CB-MOSFET) and Field plated Conventional Bulk-MOSFET (FCB-MOSFET) structures. The 4H–SiC MES–MOSFET structure consists of two additional schottky buried gates which behave like a Metal on Semiconductor (MES) at the interface of the active region and substrate. The motivation for this structure was to enhance the breakdown voltage by introducing a new technique of utilizing the reduced surface field (RESURF) concept. In our comparison and investigation we used a two-dimensional device simulator. Our simulation results show that the breakdown voltage of the proposed structure is 3.7 and 2.9 times larger than CB-MOSFET and FCB-MOSFET structures, respectively. We also showed that the threshold voltage and the slope of drain current (I_D) as a function of drain–source voltage (V_DS) for all the structures is the same.     

Studies of 6H–SiC devices

Silicon carbide (SiC) is recently receiving increased attention due to its unique electrical and thermal properties. It has been regarded as the most appropriate semiconductor material for high power, high frequency, high temperature, and radiation hard microelectronic devices. The fabrication processes and characterization of basic device on 6H–SiC were systematically studied. The main works are summarized as follows:The homoepitaxial growth on the commercially available single-crystal 6H–SiC wafers was performed in a modified gas source molecular beam epitaxy system. The mesa structured p⁺n junction diodes on the material were fabricated and characterized. The diodes showed a high breakdown voltage of 800 V at room temperature. They operated with good rectification characteristics from room temperature to 673 K.Using thermal evaporation, Ti/6H–SiC Schottky barrier diodes were fabricated. They showed good rectification characteristics from room temperature to 473 K. Using neon implantation to form the edge termination, the breakdown voltage was improved to be 800 V.n-Type 6H–SiC MOS capacitors were fabricated and characterized. Under the same growing conditions, the quality of poly-silicon gate capacitors was better than Al. In addition, SiC MOS capacitors had good tolerance to γ rays.     

Two triple points in the H2O–H2 system

Using a volumetric technique, phase transitions in the H₂O–H₂ system were investigated in the vicinity of two points of an invariant equilibrium, L+I _h+sII and L+sII+C ₁, located at 1.07 kbar and?10 °C and at 3.6 kbar and 1 °C, respectively. Liquid water (L), low-pressure hexagonal ice (I _h) and high-pressure cubic (sII) and rhombohedral (C ₁) clathrate hydrates were in equilibrium with gaseous hydrogen taken in excess.     

Space–time cloaks through birefringent Goos–H?nchen shifts

We report a theoretical demonstration for the creation of space–time holes based on birefringence of reflection,transmission, and the Goos–H?chen(GH) shifts from a chiral medium. We observed space–time holes in the reflection, transmission, and their corresponding GH-shifted beams. Two space–time holes are clearly detected in the regions of 0 t ≤ 5τ_0 and-5 w ≤ y ≤ 5 w, as well as in the regions of-5τ_0≤ t ≤ 0 and-5 w ≤ y ≤ 5 w.These space–time holes hide objects and information contents from observers and hackers. The objects and information contents are completely undetectable, and thus events can be cloaked. The results of this paper have potential applications in the invisibility of drone technology and secure communication of information in telecom industries.     

Transport properties of H–N2 mixtures

Transport coefficients (shear viscosity, volume viscosity, thermal conductivity, and mass and thermal diffusion coefficients) of H–N₂ mixtures in the dilute-gas limit have been calculated from the intermolecular potential in the temperature range 300–2000K using the classical trajectory method. The intermediate results pertaining to H–N₂ binary interactions are reported, mainly in terms of cross-section ratios. Cross-sections evaluated with the Mason–Monchick approximation yield very good results for this system, the largest deviations, about 2.5%, being observed for the thermal diffusion coefficient. The accuracy here of this approximation can primarily be attributed to a light H atom and a weakly non-spherical potential resulting in a high rotational collision number. Furthermore, we investigate to which H–N₂ cross-sections and their ratios the values of the mixture transport coefficients are most sensitive. Our results indicate that, for some cross-section ratios, reliance on universal correlations at high temperatures, often used in flame codes, can induce sizeable errors in the thermal conductivity coefficient and especially in the thermal diffusion coefficients. We also observed that the volume viscosity is particularly sensitive to the value of the cross-section for internal energy relaxation in H–N₂ collisions.     

H·A·洛伦兹:经典电子论先河的开拓者

简要介绍了科学神童H．A．洛伦兹的成才之路，以及他把经典物理学推向巅峰的显赫业绩，其中特别是电子论的成功创立．