Photochemistry in Real Space: Batho- and Hypsochromism in the Water Dimer

The development of chemical intuition in photochemistry faces several difficulties that result from the inadequacy of the one-particle picture, the Born–Oppenheimer approximation, and other basic ideas used to build models. It is shown herein how real-space approaches can be efficiently used to gain valuable insights in photochemistry through a simple example of red and blue shift effects: the double hypso- and bathochromic shifts in the low-lying valence excited states of (H₂O)₂. It is demonstrated that 1) the use of these techniques allows the perturbative language used in the theory of intermolecular interactions, even in the strongly interacting short-range regime, to be maintained; 2) one and only one molecule is photoexcited in each of the addressed excited states and 3) the electrostatic interaction between the in-the-cluster molecular dipoles provides a fairly intuitive rationalisation of the observed batho- and hypsochromism. The methods exploited and illustrated herein are able to maintain the individuality and properties of the interacting entities in a molecular aggregate, and thereby they allow chemical intuition in general states, at any geometry and using a broad variety of electronic structure methods to be kept and built.     

Porphyrin-like porous nanomaterials as drug delivery systems for ibuprofen drug

In recent years, nanomaterial-based drug delivery carriers have become some of the most attractive to be studied. The purpose of this study is to investigate the interaction of C60 fullerene, carbon nanotube and graphene having porphyrin-like FeN4 clusters with a non-steroidal anti-inflammatory drug (ibuprofen) by means of the density functional theory. Results showed that the graphene with FeN4 clusters could remarkably increase the tendency of graphene for adsorption of ibuprofen drug. Also, our ultraviolet–visible results show that the electronic spectra of the complexes exhibit a blue shift toward lower wavelengths (higher energies). It was found that Ibp/FeN4-graphene had high chemical reactivity, which was important for binding of the drug onto the target site. In order to go further and gain insight into the binding features of considered systems with ibuprofen drug, the Atoms in Molecules analysis was performed. Our results determine the electrostatic features of the Ibp/FeN4-graphene bonding. Consequently, the results demonstrated that the FeN4-graphene could be used as potential carriers for the delivery of ibuprofen drug.     

The self-assemblies of a newly designed star-shaped molecule end-capped with bromine atoms studied by scanning tunneling microscopy

A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface.We have obtained the high-resolution self-assembled STM images,from which the highly ordered and closely packed non-porous arrangements of the StOF-Br_3 molecular selfassemblies at the heptanoic acid/HOPG surface could be observed.The molecular models and selfassembled StOF-Br_3 architectures have been given in the following text.Besides,we have also figured out the surface free energy by the density functional theory(DFT) calculation,which proved that the halogen...halogen interaction was strong enough to stabilize the ordered molecular self-assemblies.This work verifies the existence of bromine...bromine interactions,and meanwhile provides a kind of effective approach for quickly building ordered molecular nanoarchitectures with large areas and different geometries.     

Crystal structures of two isostructural compounds: a second polymorph of dipotassium hydrogen citrate,K2HC6H5O7, and potassium rubidium hydrogen citrate,KRbHC6H5O7

The crystal structures of a new polymorph of dipotassium hydrogen citrate, 2K⁺·HC₆H₅O₇^2?, and potassium rubidium hydrogen citrate, K⁺·Rb⁺·HC₆H₅O₇^2?, have been solved and refined using laboratory powder X‐ray diffraction and optimized using density functional techniques. In the new polymorph of the dipotassium salt, KO₇ and KO₈ coordination polyhedra share corners and edges to form a three‐dimensional framework with channels parallel to the a axis and [111]. The hydrophobic methylene groups face each other in the channels. The un‐ionized carboxylic acid group forms a strong charge‐assisted hydrogen bond to the central ionized carboxylate group. The hydroxy group forms an intermolecular hydrogen bond to a different central carboxylate group. In the potassium rubidium salt, the K⁺ and Rb⁺ cations are disordered over two sites, in approximately 0.72:0.28 and 0.28:0.72 ratios. KO₈ and RbO₉ coordination polyhedra share corners and edges to form a three‐dimensional framework with channels parallel to the a axis. The un‐ionized carboxylic acid group forms a strong charge‐assisted hydrogen bond to an ionized carboxylate group. The hydroxy group forms an intermolecular hydrogen bond to the central carboxylate group. Density functional theory (DFT) calculations on the ordered cation structures suggest that interchange of K⁺ and Rb⁺ at the two cation sites changes the energy insignificantly.     

Temps de cohérence d'un condensat de Bose–Einstein dans un gaz isolé harmoniquement piégé

We study the condensate phase dynamics in a low-temperature equilibrium gas of weakly interacting bosons, harmonically trapped and isolated from the environment. We find that at long times, much longer than the collision time between Bogoliubov quasi-particles, the variance of the phase accumulated by the condensate grows with a ballistic term quadratic in time and a diffusive term affine in time. We give the corresponding analytical expressions in the limit of a large system, in the collisionless regime and in the ergodic approximation for the quasi-particle motion. When properly rescaled, they are described by universal functions of the temperature divided by the Thomas–Fermi chemical potential. The same conclusion holds for the mode damping rates. Such universality class differs from the previously studied one of the homogeneous gas.     

Calculations on polarization properties of alkali metal atoms using Dirac–Fock plus core polarization method

A semi-empirical atomic structure model method is developed in the framework of a relativistic case. This method starts from Dirac-Fock calculations using B-spline basis set. The core-valence electron correction is then treated in a semiempirical core polarization potential. As an application, the polarization properties of alkali metal atoms, including the static polarizabilities and long-range two-body dispersion coefficients, have been calculated. Our results are in good agreement with the results obtained from ab initio relativistic many-body perturbation method and the available experimental measurements.     

Rhorix: An interface between quantum chemical topology and the 3D graphics program blender

Chemical research is assisted by the creation of visual representations that map concepts (such as atoms and bonds) to 3D objects. These concepts are rooted in chemical theory that predates routine solution of the Schrödinger equation for systems of interesting size. The method of Quantum Chemical Topology (QCT) provides an alternative, parameter‐free means to understand chemical phenomena directly from quantum mechanical principles. Representation of the topological elements of QCT has lagged behind the best tools available. Here, we describe a general abstraction (and corresponding file format) that permits the definition of mappings between topological objects and their 3D representations. Possible mappings are discussed and a canonical example is suggested, which has been implemented as a Python “Add‐On” named Rhorix for the state‐of‐the‐art 3D modeling program Blender. This allows chemists to use modern drawing tools and artists to access QCT data in a familiar context. A number of examples are discussed. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.     

Theoretical Study on the Hydrogen Bonding Interactions in Complexes of 5‐Hydroxytryptamine with Water

The energies, geometries and harmonic vibrational frequencies of 1:1 5‐hydroxytryptamine‐water (5‐HT‐H₂O) complexes are studied at the MP2/6‐311++G(d,p) level. Natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM) analyses and the localized molecular orbital energy decomposition analysis (LMO‐EDA) were performed to explore the nature of the hydrogen‐bonding interactions in these complexes. Various types of hydrogen bonds (H‐bonds) are formed in these 5‐HT‐H₂O complexes. The intermolecular C4H5^5‐HT···O^w H‐bond in HTW3 is strengthened due to the cooperativity, whereas no such cooperativity is found in the other 5‐HT‐H₂O complexes. H‐bond in which nitrogen atom of amino in 5‐HT acted as proton donors was stronger than other H‐bonds. Our researches show that the hydrogen bonding interaction plays a vital role on the relative stabilities of 5‐HT‐H₂O complexes.     

Improved Hydrogen‐Storage Thermodynamics and Kinetics for an RbF‐Doped Mg(NH2)2–2 LiH System

The introduction of RbF into the Mg(NH₂)₂–2 LiH system significantly decreased its (de‐)hydrogenation temperatures and enhanced its hydrogen‐storage kinetics. The Mg(NH₂)₂–2 LiH–0.08 RbF composite exhibits the optimal hydrogen‐storage properties as it could reversibly store approximately 4.76 wt % hydrogen through a two‐stage reaction with the onset temperatures of 80 °C for dehydrogenation and 55 °C for hydrogenation. At 130 °C, approximately 70 % of hydrogen was rapidly released from the 0.08 RbF‐doped sample within 180 min, and the fully dehydrogenated sample could absorb approximately 4.8 wt % of hydrogen at 120 °C. Structural analyses revealed that RbF reacted readily with LiH to convert to RbH and LiF owing to the favorable thermodynamics during ball‐milling. The newly generated RbH participated in the following dehydrogenation reaction, consequently resulting in a decrease in the reaction enthalpy change and activation energy.