Dynamics of the chemical bond: inter- and intra-molecular hydrogen bond

In this discussion, we show that a static definition of a `bond' is not viable by looking at a few examples for both inter-and intra-molecular hydrogen bonding. This follows from our earlier work (Goswami and Arunan, Phys. Chem. Chem. Phys. 2009, 11, 8974) which showed a practical way to differentiate `hydrogen bonding' from `van der Waals interaction'. We report results from ab initio and atoms in molecules theoretical calculations for a series of Rg center dot center dot center dot HX complexes (Rg = He/Ne/Ar and X = F/Cl/Br) and ethane-1,2-diol. Results for the Rg center dot center dot center dot HX/DX complexes show that Rg center dot center dot center dot DX could have a `deuterium bond' even when Rg center dot center dot center dot HX is not `hydrogen bonded', according to the practical criterion given by Goswami and Arunan. Results for ethane-1,2-diol show that an `intra-molecular hydrogen bond' can appear during a normal mode vibration which is dominated by the O center dot center dot center dot O stretching, though a `bond' is not found in the equilibrium structure. This dynamical `bond' formation may nevertheless be important in ensuring the continuity of electron density across a molecule. In the former case, a vibration `breaks' an existing bond and in the later case, a vibration leads to `bond' formation. In both cases, the molecule/complex stays bound irrespective of what happens to this `hydrogen bond'. Both these cases push the borders on the recent IUPAC recommendation on hydrogen bonding (Arunan et al. Pure. Appl. Chem. 2011, 83 1637) and justify the inclusive nature of the definition.

Unusually Short Chalcogen Bonds Involving Organoselenium: Insights into the Se-N Bond Cleavage Mechanism of the Antioxidant Ebselen and Analogues

Structural studies on the polymorphs of the organoselenium antioxidant ebselen and its derivative show the potential of organic selenium to form unusually short Se center dot center dot center dot O chalcogen bonds that lead to conserved supramolecular recognition units. Se center dot center dot center dot O interactions observed in these polymorphs are the shortest such chalcogen bonds known for organoselenium compounds. The FTIR spectral evolution characteristics of this interaction from solution state to solid crystalline state further validates the robustness of this class of supramolecular recognition units. The strength and electronic nature of the Se center dot center dot center dot O chalcogen bonds were explored using high-resolution X-ray charge density analysis and atons-in-molecules (AIM) theoretical analysis. A charge density study unravels the strong electrostatic nature of Se center dot center dot center dot O chalcogen bonding and soft-metal-like behavior of organoselenium. An analysis of the charge density around Se-N and Se-C covalent bonds in conjunction with the Se center dot center dot center dot O chalcogen bonding modes in ebselen and its analogues provides insights into the mechanism of drug action in this class of organoselenium antioxidants. The potential role of the intermolecular Se center dot center dot center dot O chalcogen bonding in forming the intermediate supramolecular assembly that leads to the bond cleavage mechanism has been proposed in terms of electron density topological parameters in a series of molecular complexes of ebselen with reactive oxygen species (ROS).

The Self-Association of Graphane Is Driven by London Dispersion and Enhanced Orbital Interactions

We investigated the nature of the cohesive energy between graphane sheets via multiple CH center dot center dot center dot HC interactions, using density functional theory (DFT) including dispersion correction (Grimmes D3 approach) computations of n]graphane sigma dimers (n = 6-73). For comparison, we also evaluated the binding between graphene sheets that display prototypical pi/pi interactions. The results were analyzed using the block-localized wave function (BLW) method, which is a variant of ab initio valence bond (VB) theory. BLW interprets the intermolecular interactions in terms of frozen interaction energy (Delta E-F) composed of electrostatic and Pauli repulsion interactions, polarization (Delta E-pol), charge-transfer interaction (Delta E-CT), and dispersion effects (Delta E-disp). The BLW analysis reveals that the cohesive energy between graphane sheets is dominated by two stabilizing effects, namely intermolecular London dispersion and two-way charge transfer energy due to the sigma CH -> sigma*(HC) interactions. The shift of the electron density around the nonpolar covalent C-H bonds involved in the intermolecular interaction decreases the C-H bond lengths uniformly by 0.001 angstrom. The Delta E-CT term, which accounts for similar to 15% of the total binding energy, results in the accumulation of electron density in the interface area between two layers. This accumulated electron density thus acts as an electronic glue for the graphane layers and constitutes an important driving force in the self-association and stability of graphane under ambient conditions. Similarly, the double faced adhesive tape style of charge transfer interactions was also observed among graphene sheets in which it accounts for similar to 18% of the total binding energy. The binding energy between graphane sheets is additive and can be expressed as a sum of CH center dot center dot center dot HC interactions, or as a function of the number of C-H bonds.

The crystal structure of a lectin from Butea monosperma: Insight into its glycosylation and binding of ligands

Crystal structure of a lectin purified from Butea monosperma seeds was determined by Molecular Replacement method. Its primary structure was determined by Tandem Mass Spectroscopy and electron density maps from X-ray diffraction data. Its quaternary structure was tetrameric, formed of two monomers, alpha and beta, beta appearing as truncated alpha. The occurrence of two tetramers in the asymmetric unit of the crystal might be a consequence of asymmetric contacts due to difference in glycosylation and variable loops structures, to form an `octamer-structure'. The crystal structure showed binding pockets for gamma Abu, having a proposed role in plant defense, at the interface of canonical dimer-partners. Hemagglutination studies, enzyme kinetics, isothermal titration calorimetry and molecular dynamics showed that the lectin is specific to N-acetyl D-galactosamine, galactose and lactose in decreasing order, and alpha-amylase inhibitor. (C) 2014 Elsevier B.V. All rights reserved.

X-Ha center dot center dot center dot C hydrogen bonds in n-alkane-HX (X = F, OH) complexes are stronger than C-Ha <-X hydrogen bonds

Computational study of X-Ha <-C and C-Ha <-X hydrogen bonds in n-alkane-HX complexes (X =F,OH, alkane =propane, butane, pentane) has been carried out in this work. Ab initio and density functional theories were used for this study. For n-alkane-H2O complexes both Oa <-H-C and O-Ha <-C hydrogen bonded complex have been found, while for n-alkane-HF complexes, our attempt to optimize Fa <-H-C H-bond was not successful. Like most of the hydrogen bonded systems, strong correlation between binding energy and stretching frequency of H-F and O-H stretching mode was observed. The values of electron density and Laplacian of electron density are within the accepted range for hydrogen bonds. In all these cases, X-Ha <-C hydrogen bonds are found to be stronger than C-Ha <-X hydrogen bonds.

DECT evaluation of noncalc fied coronary artery plaque

Purpose: Composition of the coronary artery plaque is known to have critical role in heart attack. While calcified plaque can easily be diagnosed by conventional CT, it fails to distinguish between fibrous and lipid rich plaques. In the present paper, the authors discuss the experimental techniques and obtain a numerical algorithm by which the electron density (rho(e)) and the effective atomic number (Z(eff)) can be obtained from the dual energy computed tomography (DECT) data. The idea is to use this inversion method to characterize and distinguish between the lipid and fibrous coronary artery plaques. Methods: For the purpose of calibration of the CT machine, the authors prepare aqueous samples whose calculated values of (rho(e), Z(eff)) lie in the range of (2.65 x 10(23) <= rho(e) <= 3.64 x 10(23)/cm(3)) and (6.80 <= Z(eff) <= 8.90). The authors fill the phantom with these known samples and experimentally determine HU(V-1) and HU(V-2), with V-1,V-2 = 100 and 140 kVp, for the same pixels and thus determine the coefficients of inversion that allow us to determine (rho(e), Z(eff)) from the DECT data. The HU(100) and HU(140) for the coronary artery plaque are obtained by filling the channel of the coronary artery with a viscous solution of methyl cellulose in water, containing 2% contrast. These (rho(e), Z(eff)) values of the coronary artery plaque are used for their characterization on the basis of theoretical models of atomic compositions of the plaque materials. These results are compared with histopathological report. Results: The authors find that the calibration gives Pc with an accuracy of 3.5% while Z(eff) is found within 1% of the actual value, the confidence being 95%. The HU(100) and HU(140) are found to be considerably different for the same plaque at the same position and there is a linear trend between these two HU values. It is noted that pure lipid type plaques are practically nonexistent, and microcalcification, as observed in histopathology, has to be taken into account to explain the nature of the observed (rho(e), Z(eff)) data. This also enables us to judge the composition of the plaque in terms of basic model which considers the plaque to be composed of fibres, lipids, and microcalcification. Conclusions: This simple and reliable method has the potential as an effective modality to investigate the composition of noncalcified coronary artery plaques and thus help in their characterization. In this inversion method, (rho(e), Z(eff)) of the scanned sample can be found by eliminating the effects of the CT machine and also by ensuring that the determination of the two unknowns (rho(e), Z(eff)) does not interfere with each other and the nature of the plaque can be identified in terms of a three component model. (C) 2015 American Association of Physicists in Medicine.

Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.

Propagation Properties of Electromagnetic Wave in a Plasma Slab

In this paper, the calculated results about the propagation properties of electromagnetic wave in a plasma slab are described. The relationship of the propagation properties with frequencies of electromagnetic wave, and parameters of plasma (electron temperature, electron density, dimensionless collision frequency and the size of the plasma slab) is analyzed.

Investigation on Nonequlibrium Radiation and Relaxation Phenomena in Shock Tubes

The experimental results for the excited time of the nonequlibrium radiation and the ionization behind strong shock waves are presented. Using an optical multichannel analyzer, InSb infrared detectors and near-free-molecular Langmuir probes, the infrared radiation, the electron density of air and the nonequilibrium radiation spectra at different moments of the relaxation process in nitrogen test gas behind normal shock waves were obtained, respectively, in hydrogen oxygen combustion driven shock tubes.

An investigation of electromagnetic wave propagation in plasma by shock tube

This paper presents the electromagnetic wave propagation characteristics in plasma and the attenuation coefficients of the microwave in terms of the parameters n(e), v, w, L, w(b). The phi800 mm high temperature shock tube has been used to produce a uniform plasma. In order to get the attenuation of the electromagnetic wave through the plasma behind a shock wave, the microwave transmission has been used to measure the relative change of the wave power. The working frequency is f = (2 similar to 35) GHz (w = 2pif, wave length lambda = 15 cm similar to 8 mm). The electron density in the plasma is n(e) = (3 x 10(10) similar to 1 x 10(14)) cm(-3). The collision frequency v = (1 x 10(8) similar to 6 x 10(10)) Hz. The thickness of the plasma layer L = (2 similar to 80) cm. The electron circular frequency w(b) = eB(0)/m(e), magnetic flux density B-0 = (0 similar to 0.84) T. The experimental results show that when the plasma layer is thick (such as L/lambda greater than or equal to 10), the correlation between the attenuation coefficients of the electromagnetic waves and the parameters n(e), v, w, L determined from the measurements are in good agreement with the theoretical predictions of electromagnetic wave propagations in the uniform infinite plasma. When the plasma layer is thin (such as when both L and lambda are of the same order), the theoretical results are only in a qualitative agreement with the experimental observations in the present parameter range, but the formula of the electromagnetic wave propagation theory in an uniform infinite plasma can not be used for quantitative computations of the correlation between the attenuation coefficients and the parameters n(e), v, w, L. In fact, if w < w(p), v(2) much less than w(2), the power attenuations K of the electromagnetic waves obtained from the measurements in the thin-layer plasma are much smaller than those of the theoretical predictions. On the other hand, if w > w(p), v(2) much less than w(2) (just v approximate to f), the measurements are much larger than the theoretical results. Also, we have measured the electromagnetic wave power attenuation value under the magnetic field and without a magnetic field. The result indicates that the value measured under the magnetic field shows a distinct improvement.

Self-consistent kinetic modeling of low-pressure inductively coupled radio-frequency discharges

An efficient method for solving the spatially inhomogeneous Boltzmann equation in a two-term approximation for low-pressure inductively coupled plasmas has been developed. The electron distribution function (EDF), a function of total electron energy and two spatial coordinates, is found self-consistently with the static space-charge potential which is computed from a 2D fluid model, and the rf electric field profile which is calculated from the Maxwell equations. The EDF and the spatial distributions of the electron density, potential, temperature, ionization rate, and the inductive electric field are calculated and discussed. (C) 1996 American Institute of Physics.

Non-linear theory of a positive-column in a magnetic-field

A nonlinear theory of an intermediate pressure discharge column in a magnetic field is presented. Motion of the neutral gas is considered. The continuity and momentum transfer equations for charged particles and neutral particles are solved by numerical methods. The main result obtained is that the rotating velocities of ionic gas and neutral gas are approximately equal. Bohm's criterion and potential inversion in the presence of neutral gas motion are also discussed.

泰氟龙烧蚀对黏性激波层电子密度的影响

采用黏性激波层基本方程组对有无泰氟龙烧蚀两种情况下的钝锥体化学非平衡绕流作了数值求解，以研究泰氟龙烧蚀对流场电子密度的影响规律。算例结果表明：泰氟龙烧蚀确有降低流场电子密度的效应。平衡催化壁工况下这种效应的强度，显著大于非催化壁工况下的强度；远下游截面处的这种效应的强度，显著大于驻点区的强度。此外，通过计算结果分析，对形成上述影响规律的原因作了初步讨论。

YAG激光毛化技术进展

二十世纪八十年代，当比利时冶金研究中心(CRM)开发出CO_2激光毛化冷轧辊技术后，尝试用YAG激光进行轧辊毛化一直吸引着众多的研究者，这是因为YAG(1.06μm)激光波长比CO_2(10.6μm)激光波长短一个量级，材料对YAG激光有更高的吸收率，并用YAG激光可以聚焦到更小的光斑尺寸，同时使用电信号驱动的声光开关技术便于对毛化分布进行可设定控制。但是用传统声光调制的YAG激光虽然可以碇以很高的脉冲频率(>30kHz)，但单脉冲有量仅为10mJ左右，难以达到辊面毛化粗糙度的要求，因此人们认为YAG激光用于毛化的主要困难是脉冲能量太小。

Space-resolved spectral diagnosis of line-shaped laser-produced magnesium plasmas

Space-resolved spectra of line-shaped laser-produced magnesium plasmas in the normal direction of the target have been obtained using a pinhole crystal spectrograph. These spectra are treated by a spectrum analyzing code for obtaining the true spectra and fine structures of overlapped lines. The spatial distributions of electron temperature and density along the normal direction of the target surface have been obtained with different spectral diagnostic techniques. Especially, the electron density plateaus beyond the critical surface in line-shaped magnesium plasmas have been obtained with a fitting technique applied to the Stark-broadened Ly-alpha wings of hydrogenic ions. The difference of plasma parameters between those obtained by different diagnostic techniques is discussed. Other phenomena, such as plasma satellites, population inversion, etc., which are observed in magnesium plasmas, are also presented.