Hydrogen bonding in infinite hydrogen fluoride and hydrogen chloride chains

Hydrogen bonding in infinite HF and HCl bent (zigzag) chains is studied using the ab initio coupled-cluster singles and doubles (CCSD) correlation method. The correlation contribution to the binding energy is decomposed in terms of nonadditive many-body interactions between the monomers in the chains, the so-called energy increments. Van der Waals constants for the two-body dispersion interaction between distant monomers in the infinite chains are extracted from this decomposition. They allow a partitioning of the correlation contribution to the binding energy into short- and long-range terms. This finding affords a significant reduction in the computational effort of ab initio calculations for solids as only the short-range part requires a sophisticated treatment whereas the long-range part can be summed immediately to infinite distances.Comment: 9 pages, 4 figures, 3 tables, RevTeX4, corrected typo

Peierls Instabilities in Quasi-One-Dimensional Quantum Double-Well Chains

Peierls-type instabilities in quarter-filled ($\bar{n}=1/2$) and half-filled ($\bar{n}=1$) quantum double-well hydrogen-bonded chain are investigated analytically in the framework of two-stage orientational-tunnelling model with additional inclusion of the interactions of protons with two different optical phonon branches. It is shown that when the energy of proton-phonon coupling becomes large, the system undergoes a transition to a various types of insulator states. The influence of two different transport amplitudes on ground states properties is studied. The results are compared with the pressure effect experimental investigations in superprotonic systems and hydrogen halides at low temperatures.Comment: 7 pages, RevTeX, 9 eps figure

Discrete kink dynamics in hydrogen-bonded chains I: The one-component model

We study topological solitary waves (kinks and antikinks) in a nonlinear one-dimensional Klein-Gordon chain with the on-site potential of a double-Morse type. This chain is used to describe the collective proton dynamics in quasi-one-dimensional networks of hydrogen bonds, where the on-site potential plays role of the proton potential in the hydrogen bond. The system supports a rich variety of stationary kink solutions with different symmetry properties. We study the stability and bifurcation structure of all these stationary kink states. An exactly solvable model with a piecewise ``parabola-constant'' approximation of the double-Morse potential is suggested and studied analytically. The dependence of the Peierls-Nabarro potential on the system parameters is studied. Discrete travelling-wave solutions of a narrow permanent profile are shown to exist, depending on the anharmonicity of the Morse potential and the cooperativity of the hydrogen bond (the coupling constant of the interaction between nearest-neighbor protons).Comment: 12 pages, 20 figure

Electronic structure and bonding in unligated and ligated FeII porphyrins

The electronic structure and bonding in a series of unligated and ligated FeII porphyrins (FeP) are investigated by density functional theory (DFT). All the unligated four-coordinate iron porphyrins have a 3A2g ground state that arises from the (dxy)2(dz2)2(dπ)2 configuration. The calculations confirm experimental results on Fe tetraphenylporphine but do not support the resonance Raman assignment of Fe octaethylporphine as 3Eg, nor the early assignment of Fe octamethyltetrabenzporphine as 5B2g. For the six-coordinate Fe–P(L)2 (L = HCN, pyridine, CO), the strong-field axial ligands raise the energy of the Fe dz2 orbital, thereby making the iron porphyrin diamagnetic. The calculated redox properties of Fe–P(L)2 are in agreement with experiment. As models for deoxyheme, the energetics of all possible low-lying states of FeP(pyridine) and FeP(2-methylimidazole) have been studied in detail. The groundstate configuration of FeP(2-methylimidazole) was confirmed to be high-spin (dxy)2(dz2)1(dπ)2(dx2−y2)1; FeP (pyridine) is shown to be a poor model for high-spin deoxyheme. © 2002 American Institute of Physics

Impact of Leaf Removal, Applied Before and After Flowering, on Anthocyanin, Tannin, and Methoxypyrazine Concentrations in ‘Merlot’ (Vitis viniferaL.) Grapes and Wines

7siThe development and accumulation of secondary metabolites in grapes determine wine color, taste, and aroma. This study aimed to investigate the effect of leaf removal before flowering, a practice recently introduced to reduce cluster compactness and Botrytis rot, on anthocyanin, tannin, and methoxypyrazine concentrations in Merlot' grapes and wines. Leaf removal before flowering was compared with leaf removal after flowering and an untreated control. No effects on tannin and anthocyanin concentrations in grapes were observed. Both treatments reduced levels of 3-isobutyl-2-methoxypyrazine (IBMP) in the grapes and the derived wines, although the after-flowering treatment did so to a greater degree in the fruit specifically. Leaf removal before flowering can be used to reduce cluster compactness, Botrytis rot, and grape and wine IBMP concentration and to improve wine color intensity but at the expense of cluster weight and vine yield. Leaf removal after flowering accomplishes essentially the same results without loss of yield. © 2016 American Chemical Society.reservedmixedSivilotti, Paolo; Herrera, Jose Carlos; Lisjak, Klemen; Baša Česnik, Helena; Sabbatini, Paolo; Peterlunger, Enrico; Castellarin, Simone DiegoSivilotti, Paolo; Herrera, Jose Carlos; Lisjak, Klemen; Baša Česnik, Helena; Sabbatini, Paolo; Peterlunger, Enrico; Castellarin, Simone Dieg

Electronic structure and bonding in metal porphyrins, metal=Fe, Co, Ni, Cu, Zn

A systematic theoretical study of the electronic structure and bonding in metal meso-tetraphenyl porphines MTPP, M=Fe, Co, Ni, Cu, Zn has been carried out using a density functional theory method. The calculations provide a clear elucidation of the ground states for the MTPPs and for a series of [MTPP]x ions (x = 2+, 1+, 1−, 2−, 3−, 4−), which aids in understanding a number of observed electronic properties. The calculation supports the experimental assignment of unligated FeTPP as 3A2g, which arises from the configuration (dxy)2(dz2)2(dxz)1(dyz)1. The calculated M–TPP binding energies, ionization potentials, and electron affinities are in good agreement with available experimental data. The influence of axial ligands and peripheral substitution by fluorine are in accord with the experimental observation that not only half-wave potentials (E1/2) of electrode reactions, but also the site of oxidation/reduction, may be dependent on the porphyrin basicity and the type of axial ligand coordination. © 2002 American Institute of Physics

Defining the Boundaries of Development wih Plasticity

International audienceThe concept of plasticity has always been present in the history of developmental biology, both within the theory of epigenesis and within morphogenesis studies. However this tradition relies also upon a genetic conception of plasticity. Founded upon the concepts of "phenotypic plasticity" and "reaction norm," this genetic conception focuses on the array of possible phenotypic change in relation to diversified environments. Another concept of plasticity can be found in recent publications by some developmental biologists (Gilbert, West-Eberhard). I argue that these authors adopt a "broad conception of plasticity" that is closely related to a notion of development as something that is ongoing throughout an organism's lifecycle, and has no clear-cut boundaries. However, I suggest that given a narrow conception of plasticity, one can define temporal boundaries for development that are linked to specific features of the morphological process, which are different from behavioral and physiological processes