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151.
Cl, S, and P atoms have previously been shown as capable of engaging in a noncovalent bond with the N atom on another molecule. The effects of substituents B on the former atoms on the strength of this bond are examined, and it is found that the binding energy climbs in the order B = CH(3) < NH(2) < CF(3) < OH < Cl < NO(2) < F. However, there is some variability in this pattern, particularly for the NO(2) group. The A···N bonds (A = Cl, S, P) can be quite strong, amounting to as much as 10 kcal/mol. The binding energy arises from approximately equal contributions from its induction and electrostatic components, although the former becomes more dominant for the stronger bonds. The induction energy is due in large measure to the transfer of charge from the N lone pair to a B-A σ* antibonding orbital of the electron-acceptor molecule containing Cl, S, or P. These A···N bonds typically represent the lowest-energy structure on each potential energy surface, stronger than H-bonds such as NH···F, CH···N, or SH···N. 相似文献
152.
N‐Methylacetamide, a model of the peptide unit in proteins, is allowed to interact with CH3SH, CH3SCH3, and CH3SSCH3 as models of S‐containing amino acid residues. All of the minima are located on the ab initio potential energy surface of each heterodimer. Analysis of the forces holding each complex together identifies a variety of different attractive forces, including SH???O, NH???S, CH???O, CH???S, SH???π, and CH???π H‐bonds. Other contributing noncovalent bonds involve charge transfer into σ* and π* antibonds. Whereas some of the H‐bonds are strong enough that they represent the sole attractive force in several dimers, albeit not usually in the global minimum, charge‐transfer‐type noncovalent bonds play only a supporting role. The majority of dimers are bound by a collection of several of these attractive interactions. The SH???O and NH???S H‐bonds are of comparable strength, followed by CH???O and CH???S. 相似文献
153.
Two 3D porous terbium(III) mucicate frameworks, {[Tb(2)(Mu(2-))(3)(H(2)O)(2)]·4H(2)O}(n) (1) and {[Tb(Mu(2-))(Ox(2-))(0.5)(H(2)O)]·H(2)O}(n) (2), have been synthesized under hydrothermal conditions by changing the pH of the reaction medium. Isostructural europium(III) and seven mixed terbium(III)-europium(III) mucicates were synthesized by doping different percentages of Eu(III) under similar reaction conditions and unveiling different emission colors ranging from green to red under the same wavelength. Both dehydrated Tb(III) metal-organic frameworks exhibit selective H(2)O vapor sorption over other solvent molecules (MeOH, MeCN, and EtOH) of less polarity and bigger size and have been correlated to the highly hydrophilic pore surfaces decorated with -OH groups and O atoms from the carboxyl groups of mucicate. 相似文献
154.
We follow a suggestion by Lipoff and Herschbach [Mol. Phys. 108, 1133 (2010)] and compare dressed and bare adiabatic potentials to get insight regarding the low-energy dynamics (e.g., cold reaction) taking place in molecular systems. In this particular case, we are interested to study the effect of conical intersections (ci) on the interacting atoms. For this purpose, we consider vibrational dressed adiabatic and vibrational dressed diabatic potentials in the entrance channel of reactive systems. According to our study, the most one should expect, in case of F + H(2), is a mild effect of the (1, 2) ci on its reactive/exchange process--an outcome also supported by experiment. This happens although the corresponding dressed and bare potential barriers (and the corresponding van der Waals potential wells) differ significantly from each other. 相似文献
155.
The interfacial properties as reflected in the interfacial tension values and the density profile of Morse fluids has been studied. The parameter range is chosen to coincide with that describing the behaviour of solid metals. The interfacial tension has been found to follow Guggenheim's and MacLeod's relations. However, the constants, while independent of temperature for each metal, are not the universal values predicted; with the exception of Macleod's exponent p. The density profile illustrates the change in densities across the interface dividing the coexisting vapour and liquid phases. The correlation length is also found to follow the universal relation with temperature, but again the constants, while independent of temperature, are dependent on the type of metal. The value of constant ν is found to be different for all five metals considered and is found to differ from the three-dimensional Ising model value of ν?=?0.630, which is also predicted by applying the Lennard–Jones model. 相似文献
156.
Pradip Kar Narayan C. Pradhan Basudam Adhikari 《Journal of Macromolecular Science: Physics》2013,52(4):669-679
Poly(m-aminophenol) was synthesized chemically from aqueous solutions of the monomer meta-aminophenol (mAP) in the initially acidic or basic medium by using ammonium persulfate as an oxidant. The polymer (PmAPA) synthesized in initially aqueous HCl medium was insoluble in organic solvents even after dedoping, while the polymer (PmAPB) synthesized in initially aqueous NaOH solution was found to be soluble in high pH water, dimethyl sulfoxide (DMSO), and dimethylformamide. It was possible to obtain a stable, free-standing film from the DMSO solution of PmAPB but, due to insolubility and infusibility, film casting was not possible for PmAPA. The synthesized polymers were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analyses, X-ray diffraction spectroscopy, and four-probe DC electrical conductivity. A ladder-type structure was formed during the chemical polymerization of mAP in aqueous HCl, while a hydroxyl derivative of polyaniline was obtained in aqueous NaOH. The conductivity of sulfuric acid-doped PmAPB was 104 times higher than that of in situ HCl-doped PmAPA. An explanation of the difference in properties of both polymers is given based on molecular modeling. 相似文献
157.
Kaphle GC Ganguly S Banerjee R Banerjee R Khanal R Adhikari CM Adhikari NP Mookerjee A 《J Phys Condens Matter》2012,24(29):295501
In this paper we shall study three binary alloy systems, one constituent of which is Mn. The other constituents are chosen from a particular column of the periodic table: Ni(3d), Pt (4d) and Pd (5d). As we go down the column, the d-bands become wider, discouraging spin-polarization. In a disordered alloy, the situation becomes more complicated, as the exchange interaction between two atoms is environment dependent. We shall compare and contrast their magnetic behaviour using robust electronic structure techniques. In all three alloy systems conjectures are made to explain experimental data. In this paper we shall examine whether there is any basis to these conjectures. 相似文献
158.
Grzegorz Litak Michael I. Friswell Cedrick A. Kitio Kwuimy Sondipon Adhikari Marek Borowiec 《力学快报》2012,2(4):043009
We examine an energy harvesting system of two magnetopiezoelastic oscillators coupled by electric circuit and driven by harmonic excitation. We focus on the effects of synchronization and escape from a single potential well. In the system with relative mistuning in the stiffness of the harvesting oscillators, we show the dependence of the voltage output for different excitation frequencies. 相似文献
159.
P. Poornesh G. Umesh P. K. Hegde M. G. Manjunatha K. B. Manjunatha A. V. Adhikari 《Applied physics. B, Lasers and optics》2009,97(1):117-124
We report here the studies on third-order nonlinear optical properties of two novel polythiophene composite films investigated
using the Z-scan technique. The measurements were carried out using a Q-switched, frequency doubled Nd:YAG laser producing
7 nanosecond laser pulses at 532 nm. Z-scan results reveal that the composite films exhibit self-defocusing nonlinearity.
The real and imaginary parts of the third-order nonlinear optical susceptibility were of the order 10−12 esu. The effective excited-state absorption cross section was found to be larger than the ground state absorption cross section,
indicating that the operating nonlinear mechanism is reverse saturable absorption (RSA). The polythiophene composite films
also exhibit good optical power limiting of the nanosecond laser pulses. The nonlinear optical parameters are found to increase
on increasing the strength of the electron-donor group, indicating the dependence of χ
(3) on the electron-donor/acceptor units of polythiophenes. 相似文献
160.
Anup K. Adhikari Christoph G. P. Ziegler Kai Schwedtmann Clemens Taube Jan. J. Weigand Robert Wolf 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(51):18757-18763
The chemistry of polyphosphorus cations has rapidly developed in recent years, but their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P5R2]+ cations with cyclopentadienyl metal complexes. The reaction of [CpArFe(μ‐Br)]2 (CpAr=C5(C6H4‐4‐Et)5) with [P5R2][GaCl4] (R=iPr and 2,4,6‐Me3C6H2 (Mes)) afforded bicyclo[1.1.0]pentaphosphanes ( 1‐R , R=iPr and Mes), showing an unsymmetric “butterfly” structure. The same products 1‐R were formed from K[CpAr] and [P5R2][GaCl4]. The cationic complexes [CpArCo(η4‐P5R2)][GaCl4] ( 2‐R [GaCl4], R=iPr and Cy) and [(CpArNi)2(η3:3‐P5R2)][GaCl4] ( 3‐R [GaCl4]) were obtained from [P5R2][GaCl4] and [CpArM(μ‐Br)]2 (M=Co and Ni) as well as by using low‐valent “CpArMI” sources. Anion metathesis of 2‐R [GaCl4] and 3‐R [GaCl4] was achieved with Na[BArF24]. The P5 framework of the resulting salts 2‐R [BArF24] can be further functionalized with nucleophiles. Thus reactions with [Et4N]X (X=CN and Cl) give unprecedented cyano‐ and chloro‐functionalized complexes, while organo‐functionalization was achieved with CyMgCl. 相似文献