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1.
Carbon coatings were deposited by atmospheric plasma jet. Influence of the distance between the exit of the plasma gun and a substrate (consequently temperature of the substrate) on properties of the coatings was investigated. The coatings deposited near to the exit of the plasma gun are porous with columnar structure, moderate hardness (∼10 GPa), and the lowest hydrogen (∼7 at.%) concentration. The coatings deposited at the larger standoff distance (>5 mm) have higher hydrogen (≤25 at.%) content and graphite-like structure. Most of the hydrogen in all coatings is bonded to the sp3 carbon (70-60 at.%) and predominantly forms methylene compounds. Decrease of standoff distance yields lower concentration of sp3 CH3 compounds and relative increase of amount of hydrogenated sp2 rings. 相似文献
2.
Eriksen JJ Olsen JM Aidas K Ågren H Mikkelsen KV Kongsted J 《Journal of computational chemistry》2011,32(13):2853-2864
In this study, we have applied two different spanning protocols for obtaining the molecular conformations of L-tryptophan in aqueous solution, namely a molecular dynamics simulation and a molecular mechanics conformational search with subsequent geometry re-optimization of the stable conformers using a quantum mechanically based method. These spanning protocols represent standard ways of obtaining a set of conformations on which NMR calculations may be performed. The results stemming from the solute-solvent configurations extracted from the MD simulation at 300 K are found to be inferior to the results stemming from the conformations extracted from the MM conformational search in terms of replicating an experimental reference as well as in achieving the correct sequence of the NMR relative chemical shifts of L-tryptophan in aqueous solution. We find this to be due to missing conformations visited during the molecular dynamics run as well as inaccuracies in geometrical parameters generated from the classical molecular dynamics simulations. 相似文献
3.
The H-bonded complexes of pyridine N-oxide (PyO) with H(2)O, acetic, cyanoacetic, propiolic, tribromoacetic, trichloroacetic, trifluoroacetic, hydrochloric, and methanesulfonic acids have been studied by FTIR and NMR spectroscopy, X-ray diffraction, and quantum chemical DFT calculations. Correlations between vibrational frequencies of the NO stretching and PyO ring modes and geometric parameters of the H-bond have been established. FTIR experiments show and DFT calculations confirm that definite discontinuity is present in the vicinity of the midpoint in the proton transfer pathway. The established correlations significantly aid in the understanding of fine effects such as the isotope (deuteration) effect, crystal-to-solution transition, or criticality of aqueous solutions induced by ionic pairs. Geometric isotope effect in the ionic H-bond aggregate of PyO·H(D)Cl was found to be extraordinary large. Measured FTIR, CP/MAS, and high-resolution (13)C NMR spectra indicate that H-bond in the PyO·HCl complex in polar solvent can potentially be more ionic than in the crystal. Vibrational modes of ionic pairs originating via proton transfer in H-bond complexes can provide new information concerning the interionic interaction and its role in the phase separation and mezo-structuring processes. The results are compared to the relevant data for PyO·HCl complex in argon matrix. 相似文献
4.
Balevicius V Aidas K Tamuliene J Fuess H 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(5):835-839
Moderately narrow 1H NMR signals were observed in the solid-phase obtained from pyridine-N-oxide (PyO)...HCl solutions in acetonitrile/H2O after heterogeneous phase separation. High-resolution 1H NMR spectra are compared with those of crystalline PyO...HCl and PyO...DCl. It is concluded that partially resolved peaks in 1H NMR spectra of solids are related with heterogeneity of the spin system and the presence of different mobile H-bond clusters containing PyO, HCl, DCl and water molecules. Some part of non-bonded water or HCl molecules is captured in the cavities of crystalline samples. The attribution of the 1H NMR signals was based on the density functional theory calculation of proton magnetic screening tensor of the most expected H-bond structures in the 6-311G** basis taking into account the solvent effect by the polarized continuum model. 相似文献
5.
Balevicius V Bariseviciute R Aidas K Svoboda I Ehrenberg H Fuess H 《Physical chemistry chemical physics : PCCP》2007,9(24):3181-3189
In this work the role of higher molecular aggregation in the proton transfer processes within hydrogen bond (H-bond) is investigated. The H-bonded complex consisting of 4-cyanopyridine (CyPy) with trichloroacetic acid (TCA) has been studied in the solutions of acetonitrile, carbon tetrachloride, chloroform and dichloroethane as solvent by FTIR spectroscopy and quantum chemical DFT calculations. In order to illustrate the effect of increasing H-bond strength FTIR investigations have also been performed on solutions of CyPy with H(2)O, acetic-, trifluoroacetic- and methanesulfonic acids. Proton states in the H-bond have been monitored using vibrational CyPy ring modes in FTIR spectra. The stabilization of the CyPy/TCA complex in its protonated form upon increasing polarity of the solvent has been evidenced. It was shown that formation of the CyPy/(TCA)(2) aggregates in the solutions favors the proton transfer process. An X-ray diffraction study has been performed on a single 1 : 2 co-crystal of pyridine/3,5-dinitrobenzoic acid. The H-bond motif found in this system exhibits the same connectivity by strong hydrogen bonds N-H(+)[dot dot dot]O(-) and O-H[dot dot dot]O as that in the CyPy/(TCA)(2) complex predicted by DFT calculation. Certain discrepancies are observed in C-H[dot dot dot]O connectivity only. The networks of H-bonds in both assemblies differ from those usually pictured for 1 : 2 base/carboxylic acid complexes in the literature. 相似文献
6.
NA Murugan K Aidas J Kongsted Z Rinkevicius H Agren 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(37):11677-11684
Herein, we explore the use of spin-spin coupling constants (SSCCs) in merocyanine (MCYNE) dyes as indicators of polarity. For this purpose, we use Car-Parrinello hybrid quantum mechanics/molecular mechanics (QM/MM) to determine the structures of MCYNE in solvents of different polarity, followed by computations of the SSCCs by using QM/MM linear-response theory. The molecular geometry of MCYNE switches between neutral, cyanine-like, and zwitterionic depending on the polarity of the solvent. This structural variation is clearly reflected in the proton SSCCs in the polymethine backbone, which are highly sensitive to the dielectric nature of the environment; this mechanism can be used as a "polarity indicator" for different microenvironments. This result is highlighted by computing the SSCCs of the MCYNE probe in the cavity of the beta-lactoglobulin protein. The computed SSCCs clearly indicate a non-polar hydrophobic dielectric nature of this cavity. 相似文献
7.
The amorphous hydrogenated carbon films (a-C:H) were obtained on Si (1 1 1) wafers by plasma jet chemical vapor deposition (PJCVD). a-C:H coatings have been prepared at 1000 Pa in argon/acetylene mixture. The Ar/C2H2 gas volume ratio varied from 1:1 to 8:1. It was demonstrated that by varying the Ar/C2H2 ratio the composition, growth rate of the coatings, and consequently the structure of the film, can be controlled. The growth rate and surface porosity of coatings deposited at Ar/C2H2 = 8:1 ratio decrease slightly with an increase in the distance between the plasma torch nozzle and substrate from 0.04 to 0.095 m. The transmittance of the coatings in the IR region of 2.5–25 μm slightly increases, while the absorption peaks at 2850–2960 cm?1 related with sp3 CH2–3 modes remain unchanged with an increase in the distance. The Raman spectroscopy indicated that the a-C:H coating formed at the Ar/C2H2 = 8:1 and 0.06 m has the highest sp3 C–C fraction. The proposed PJCVD technique allows to achieve the growth rates up to 300 nm/s. 相似文献
8.
Mattias Kalén Elisabet Wallgard Noomi Asker Aidas Nasevicius Elisabet Athley Erik Billgren Jon D. Larson Shannon A. Wadman Elizabeth Norseng Karl J. Clark Liqun He Linda Karlsson-Lindahl Ann-Katrin Häger Holger Weber Hellmut Augustin Tore Samuelsson Chelsy K. Kemmet Carly M. Utesch Jeffrey J. Essner Perry B. Hackett Mats Hellström 《Chemistry & biology》2009,16(4):432-441
9.
Dr. N. Arul Murugan Dr. Kestutis Aidas Dr. Jacob Kongsted Dr. Zilvinas Rinkevicius Prof. Dr. Hans Ågren 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(37):11677-11684
Herein, we explore the use of spin–spin coupling constants (SSCCs) in merocyanine (MCYNE) dyes as indicators of polarity. For this purpose, we use Car–Parrinello hybrid quantum mechanics/molecular mechanics (QM/MM) to determine the structures of MCYNE in solvents of different polarity, followed by computations of the SSCCs by using QM/MM linear‐response theory. The molecular geometry of MCYNE switches between neutral, cyanine‐like, and zwitterionic depending on the polarity of the solvent. This structural variation is clearly reflected in the proton SSCCs in the polymethine backbone, which are highly sensitive to the dielectric nature of the environment; this mechanism can be used as a “polarity indicator” for different microenvironments. This result is highlighted by computing the SSCCs of the MCYNE probe in the cavity of the beta‐lactoglobulin protein. The computed SSCCs clearly indicate a non‐polar hydrophobic dielectric nature of this cavity. 相似文献
10.
V. Nagirnyi G. Geoffroy R. Grigonis S. Guizard M. Kirm A. Kotlov L.L. Nagornaya M. Nikl V. Sirutkaitis S. Vielhauer 《Radiation measurements》2010,45(3-6):262-264
The relaxation of electronic excitations in CdWO4 and CaWO4 crystals was studied using the method of time-resolved interferometry with 100-fs temporal resolution at temperatures 15–295 K. The electronic system was excited in the one-photon and two-photon regime within the excitonic band in CaWO4 and in the electron-hole continuum in CdWO4. Immediate trapping of charge carriers was detected under pumping in the excitonic band of CaWO4. This result is in agreement with decay kinetics measurements with nanosecond time resolution under direct creation of excitons by 100-fs laser pulses. Fast relaxation of charge carriers followed by formation of excitons was observed in CdWO4. The comparison with previous work allows suggesting the formation of bulk excitons and surface-perturbed excitons in the multi-photon and one-photon regime. The corresponding models of self-trapped exciton creation in tungstate crystals are discussed. 相似文献