Sublimation Properties of α,ω-Diamines Revisited from First-Principles Calculations

Sublimation enthalpies of alkane-α,ω-diamines exhibit an odd-even pattern within their homologous series. First-principles calculations coupled with the quasi-harmonic approximation for crystals and with the conformation mixing model for the ideal gas are used to explain this phenomenon from the theoretical point of view. Crystals of the odd and even alkane-α,ω-diamines distinctly differ in their packing motifs. However, first-principles calculations indicate that it is a delicate interplay of the cohesive forces, phonons, molecular vibrations and conformational equilibrium which governs the odd-even pattern of the sublimation enthalpies within the homologous series. High molecular flexibility of the alkane-α,ω-diamines predetermines higher sensitivity of the computational model to the quality of the optimized geometries and relative conformational energies. Performance of high-throughput computational methods, such as the density functional tight binding (DFTB, GFN2-xTB) and the explicitly correlated dispersion-corrected Møller - Plesset perturbative method (MP2C-F12), are benchmarked against the consistent state-of-the-art calculations of conformational energies and interaction energies, respectively.     

Cyanine-Flavonol Hybrids for Near-Infrared Light-Activated Delivery of Carbon Monoxide

Carbon monoxide (CO) is an endogenous signaling molecule that controls a number of physiological processes. To circumvent the inherent toxicity of CO, light-activated CO-releasing molecules (photoCORMs) have emerged as an alternative for its administration. However, their wider application requires photoactivation using biologically benign visible and near-infrared (NIR) light. In this work, a strategy to access such photoCORMs by fusing two CO-releasing flavonol moieties with a NIR-absorbing cyanine dye is presented. These hybrids liberate two molecules of CO in high chemical yields upon activation with NIR light up to 820 nm and exhibit excellent uncaging cross-sections, which surpass the state-of-the-art by two orders of magnitude. Furthermore, the biocompatibility and applicability of the system in vitro and in vivo are demonstrated, and a mechanism of CO release is proposed. It is hoped that this strategy will stimulate the discovery of new classes of photoCORMs and accelerate the translation of CO-based phototherapy into practice.     

Isomorphic edge disjoint subgraphs of hypergraphs

We show that any k‐uniform hypergraph with n edges contains two isomorphic edge disjoint subgraphs of size for k = 4, 5 and 6. This is best possible up to a logarithmic factor due to an upper bound construction of Erd?s, Pach, and Pyber who show there exist k‐uniform hypergraphs with n edges and with no two edge disjoint isomorphic subgraphs with size larger than . Furthermore, our result extends results Erd?s, Pach and Pyber who also established the lower bound for k = 2 (eg. for graphs), and of Gould and Rödl who established the result for k = 3. © 2016 Wiley Periodicals, Inc. Random Struct. Alg., 48, 767–793, 2016     

On induced Ramsey numbers for k‐uniform hypergraphs

Let denote the complete k‐uniform k‐partite hypergraph with classes of size t and the complete k‐uniform hypergraph of order s. One can show that the Ramsey number for and satisfies when t = s^o(1) as s →∞. The main part of this paper gives an analogous result for induced Ramsey numbers: Let be an arbitrary k‐partite k‐uniform hypergraph with classes of size t and an arbitrary k‐graph of order s. We use the probabilistic method to show that the induced Ramsey number (i.e. the smallest n for which there exists a hypergraph such that any red/blue coloring of yields either an induced red copy of or an induced blue copy of ) satisfies . © 2015 Wiley Periodicals, Inc. Random Struct. Alg., 48, 5–20, 2016     

Incidence properties of cosets in loops

We study incidence properties among cosets of infinite loops, with emphasis on well‐structured varieties such as antiautomorphic loops and Bol loops. While cosets in groups are either disjoint or identical, we find that the incidence structure in general loops can be much richer. Every symmetric design, for example, can be realized as a canonical collection of cosets of a infinite loop. We show that in the variety of antiautomorphic loops the poset formed by set inclusion among intersections of left cosets is isomorphic to that formed by right cosets. We present an algorithm that, given a infinite Bol loop S, can in some cases determine whether |S| divides |Q| for all infinite Bol loops Q with S?Q, and even whether there is a selection of left cosets of S that partitions Q. This method results in a positive confirmation of Lagrange's Theorem for Bol loops for a few new cases of subloops. Finally, we show that in a left automorphic Moufang loop Q (in particular, in a commutative Moufang loop Q), two left cosets of S?Qare either disjoint or they intersect in a set whose cardinality equals that of some subloop of S.     

Infrared optical constants of n-type silicon

The infrared optical constants of n-type Si are determined from reflectance and transmittance spectra. The Drude formula with empirically adjusted, concentration dependent, parameters is used. Its low-wavelength limit is in agreement with recent mobility results. A pronounced difference between As-, P-, and Sb-doped Si is found for the free electron concentration above 10¹⁹ cm^–3. Simple empirical formulae are given for the optical constants as functions of both wavenumber and concentration.     

Eine vollständige CNDO/2-CI Berechnung von H2O und H2O+

Zusammenfassung Für die Moleküle H₂O und H₂O⁺ wurde unter Verwendung von zusätzlichen Operatoren, die untereinander und mit dem CNDO-Hamiltonoperator kommutieren, eine vollständige CNDO/2-CI Berechnung des Grundzustandes und der angeregten Zustände durchgeführt.

---

Full CNDO/2-CI calculation on H₂O and H₂O⁺

Using additional normal constants of motion of the CNDO-Hamilton operator, full CNDO/2-CI calculations of the ground and excited states for the molecules H₂O and H₂O⁺ were performed.

---

Résumé Calculs complets CNDO/2-CI des états fondamentaux et excités des molécules H₂O et H₂O⁺, en utilisant des constantes normales du mouvement associées à l'hamiltonien CNDO.

---

---

Für das freundliche Durchlesen des Manuskriptes danken wir den Herren Dr. J. Fabian, Dr. A. Mehlhorn und Dipl. Chem. J. Kuhn.

---

Für die gewährte Unterstützung sind wir den Herren Doz. R. Zahradník und Dr. M, Tomáek zu Dank verpflichtet.     

Cubic-grid Gaussian basis sets for electron scattering calculations IV

Summary An analytical formula has been derived for averaging the differential cross section for electron scattering with respect to isotropic target molecule orientation. It may be applied to any type ofT-matrix element k ^out|T|k ⁱⁿ in which the plane-wave functionsk ^out andk ⁱⁿ are expanded in a set ofs-type Gaussian functions. The formula for averaging was tested against results obtained by Monte-Carlo-type calculations and against experimental data for elastic electron scattering by the H₂ molecule.