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1.
Basem Kanawati Dieter Lenoir Philippe Schmitt‐Kopplin 《Journal of Physical Organic Chemistry》2011,24(2):83-91
The reaction channels of di‐tert‐butylcarbene ( 2 ), its radical anion, ( 3 ) and its radical cation ( 4 ) were investigated theoretically by using DFT/B3LYP with 6‐31+G(d) basis set and 6‐311+G(2d,p) for single point energy calculations. Conversion of the neutral carbene 2 to the charged species 3 and 4 results in significant geometric changes. In cation 4 two different types of C? (CH3)3 bonds are observed: one elongated sigma bond called “axial” with 1.61 Å and two normal sigma bonds with a bond length of 1.55 Å. Species 2 and 4 have an electron deficient carbon center; therefore, migration of CH3 and H is observed from adjacent tert‐butyl groups with low activation energies in the range of 6–9 kcal/mol like similar Wagner–Meerwein rearrangements in the neopentyl‐cation system. Neutral carbene 2 shows C? H insertion to give a cyclopropane derivative with an activation energy of 6.1 kcal/mol in agreement with former calculations. Contrary to species 2 and 4 , the radical anion 3 has an electron rich carbon center which results in much higher calculated activation energies of 26.3 and 42.1 kcal/mol for H and CH3 migrations, respectively. NBO charge distribution indicates that the hydrogen migrates as a proton. The central issue of this work is the question: how can tetra‐tert‐butylethylene ( 1 ) be prepared from reaction of either species 2 , 3 , or 4 as precursors? The ion–ion reaction between 3 and 4 to give alkene 1 with a calculated reaction enthalpy of 203.5 kcal/mol is extremely exothermic. This high energy decomposes alkene 1 after its formation into two molecules of carbene 2 spontaneously. Ion–molecule reaction of radical anion 3 with the neutral carbene 2 is a much better choice: via a proper oriented charge–transfer complex the radical anion of tetra‐tert‐butylethylene (11) is formed. The electron affinity of 1 was calculated to be negligible. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
2.
Bin Dong Yurui Fang Lixin Xia Hongxing Xu Mengtao Sun 《Journal of Raman spectroscopy : JRS》2011,42(6):1205-1206
For the first time, the experimental and theoretical evidence for the conversion of 4‐nitrobenzenethiol (4‐NBT) to p,p′‐dimercaptoazobenzene (DMAB) in Ag and Cu sols by surface photochemistry reaction is obtained with surface‐enhanced Raman scattering (SERS) spectroscopy. The SERS spectrum of 4‐NBT in Cu sol is identical to that of DMAB produced from 4‐aminothiophenol in Ag sol as reported in recent literature, thereby providing direct spectral evidence. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
3.
M. Sigalov B. Shainyan N. Chipanina I. Ushakov A. Shulunova 《Journal of Physical Organic Chemistry》2009,22(12):1178-1187
2‐(Pyrrol‐2‐ylmethylene)‐1,3‐indandione ( 4 ) and 2‐(pyrrol‐2‐ylmethylene)‐3‐dicyanomethylidene‐1‐indanone ( 5 ) were synthesized. Multinuclear and 2D‐NMR, IR, UV spectroscopic investigations as well as quantum chemical calculations showed the presence of strong hydrogen bonding in these molecules. For both molecules, the presence of two conformers, with and without H‐bond, was experimentally detected in the basic solvents (DMSO, acetone, pyridine) and the solvate complexes were theoretically calculated. Specific behavior of the intramolecular H‐bonded complexes different from that of the intermolecular H‐complexes is discussed. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
4.
The polarized Raman spectra of the oriented single crystals of L ‐ and DL ‐alanine, α‐, β‐ and γ‐polymorphs of glycine have been studied at 3–300 K. Regularly spaced band packets have been observed in the spectral range of 2500–3000 cm−1, with intensity decreasing noticeably on heating. These band packets were interpreted as the manifestations of the existence of N H self‐trapped states in these systems at low temperatures. The analysis of the polarized spectra has shown that the self‐trapping is observed exclusively for the NH stretching vibration of the amino groups, which is related to the NH···O hydrogen bonds along the head‐to‐tail chains of zwitterions in the crystal structures. The wavenumber of this NH stretching vibration, however, was proposed to depend not solely on the length of this NH···O hydrogen bond, but also on the lengths of all the other NH···O hydrogen bonds formed by the NH3+ and the COO− groups in the structure linking the head‐to‐tail chains with each other. The arguments in favor of the hypothesis that the self‐trapping in these systems can be mediated by zero‐point quantum motions, and not by lattice phonons, are considered. The unusually low wavenumber (2500 cm−1) observed for the NH stretching vibration and indicating at the formation of a very strong NH···O bond is interpreted based on considering the effect of the crystalline environment on the formation and properties of the NH···O bonds in the head‐to‐tail chains of amino acid zwitterions. The results are interesting for understanding the factors determining the dynamics and structural instability of crystalline amino acids and also for biophysical chemistry, as the hydrogen bonded chains formed by amino acid zwitterions in the crystals can mimic the peptide chains. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
5.
The formation of N‐trifluoromethylsulfonyl‐2‐vinylaziridine and N‐trifluoromethylsulfonyl‐3‐pyrroline by the reaction of the singlet and triplet trifluoromethanesulfonylnitrenes with s‐cis‐ and s‐trans‐1,3‐butadienes was studied theoretically at the B3LYP/6‐311++G(d,p) and M06‐2X/6‐311++G(d,p) levels of theory. The singlet trifluoromethanesulfonylnitrene adds to s‐cis‐ and s‐trans‐1,3‐butadiene exothermally in one step to give the product of 1,2‐cycloaddition, N‐trifluoromethylsulfonyl‐2‐vinylaziridine, the energy decreasing by 88.5 and 86.2 kcal/mol at the B3LYP level and by 105.2 and 103.0 kcal/mol at the M06‐2X level, respectively. The formed 2‐vinylaziridine can undergo rotation about the C(2)–Csp2 bond with the barrier not exceeding 3.5 kcal/mol and to rearrange into N‐trifluoromethylsulfonyl‐3‐pyrroline. The triplet trifluoromethanesulfonylnitrene reacts with s‐cis‐ and s‐trans‐1,3‐butadiene in two steps. The first exothermic step is the formation of the triplet diradical adducts. The second step is the spin inversion with the energy raising by 5.8 and 17.8 kcal/mol at the B3LYP level and by 11.0 and 20.8 kcal/mol at the M06‐2X level for the adducts to s‐cis‐ and s‐trans‐1,3‐butadiene, respectively. Recombination of the radical centers occurs selectively to give N‐trifluoromethylsulfonyl‐2‐vinylaziridine that is exothermally rearranged into N‐trifluoromethylsulfonyl‐3‐pyrroline with the energy barrier of 40 kcal/mol at the B3LYP level and of 50 kcal/mol at the M06‐2X level. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
6.
Takashi Yamamoto 《X射线光谱测定》2008,37(6):572-584
The characteristics of pre‐edge peaks in K‐edge x‐ray absorption near edge structure (XANES) spectra of 3d transition metals were reviewed from viewpoints of the selection rule, coordination number, number of d‐electrons, and symmetry of the coordination sphere. The contribution of the electric dipole and quadrupole transition to the peaks was discussed on the basis of the group theory, polarized spectra, and theoretical calculations. The pre‐edge peak intensity for Td symmetry is larger than those for Oh symmetry for all 3d elements. The intense pre‐edge peak for tetrahedral species of 3d transition metals is not due to 1s–3d transition, but transition to the p component in d–p hybridized orbital. The mixing of metal 4p orbitals with the 3d orbitals depends strongly on the coordination symmetry, and the possibility is predictable by group theory. The transition of 1s electron to d orbitals is electric quadrupole component in any of the symmetries. The d–p hybridization does not occur with regular octahedral symmetry, and the weak pre‐edge peak consists of 1s–3d electric quadrupole transition. The pre‐edge peak intensity for a compound with a tetrahedral center changes as a function of the number of 3d electrons regardless of the kind of element; it is maximized at d0 and gradually decreases to zero at d10. The features of pre‐edge peaks in K‐edge XANES spectra for 4d elements and the L1‐edge for 5d elements are analogous with those for 3d elements, but the pre‐edge peak is broadened due to the wide natural width of the core level. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
7.
What are the correct L‐subshell photoionization cross sections for quantitative X‐ray spectroscopy?
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For fundamental parameter‐based, quantitative X‐ray fluorescence, X‐ray photoelectron spectroscopy or Auger electron spectroscopy, it is crucial to accurately know the photoionization cross sections (PCS). This atomic probability to absorb the exciting photon and eject a photoelectron, in general, followed by a subsequent decay resulting in the emission of a fluorescence photon or an Auger electron, strongly depends on the electron configuration and photon energy. Two contrary models for the photon energy dependence of the L‐subshell PCS, or the 2s, 2p ½ and 2p 3/2; energy levels, respectively, exist in the literature, and an experimental verification was not available until recently. In this work, the two models for calculating the PCS are discussed, and their influence on quantitative experiments is demonstrated by means of the fluorescence production cross sections for the three L shells. Depending on the excitation conditions, these fluorescence production cross sections and, thus, the derived quantitative results can differ significantly if the wrong PCS model is employed. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
8.
Damian Jankowski Roman
wietlik Eric W. Reinheimer Marc Fourmigu 《Journal of Raman spectroscopy : JRS》2011,42(7):1518-1527
We report on the infrared (IR) and Raman studies of the three isostructural quasi‐one‐dimensional cation radical salts of 3,4‐dimethyl‐tetrathiafulvalene (o‐DMTTF)2X (X = Cl, Br, and I), which all exhibit metallic properties at room temperature and undergo transitions to a semiconducting state in two steps: a soft metal‐to‐semiconductor regime change in the temperature region Tρ = 5–200 K and then a sharp phase transition at about TMI = 50 K. Polarized IR reflectance spectra (700–16 000 cm−1) and Raman spectra (50–3500 cm−1, excitation λ = 632.8 nm) of single crystals were measured as a function of temperature (T = 5–300 K) to assess the eventual formation of a charge‐ordered state below 50 K. Additionally, the temperature dependence of the IR absorption spectra of powdered crystals in KBr discs was also studied. The Raman spectra and especially the bands related to the CC stretching vibration of o‐DMTTF provide unambiguous evidence of uniform charge distribution on o‐DMTTF down to the lowest temperatures, without any modification below 50 K. However, the temperature dependence of Raman spectra indicates a regime change below about 200 K. Temperature dependence of both electronic dispersion and vibrational features observed in the IR spectra also clearly confirms the regime change below about 200 K and shows the involvement of C H···X hydrogen bonds in the electronic localization; some spectral changes can be also related with the phase transition at 50 K. Additionally, using density functional theory methods, the normal vibrational modes of the neutral o‐DMTTF0 and cationic o‐DMTTF+ species, as well as their theoretical IR and Raman spectra, were calculated. The theoretical data were compared with the experimental IR and Raman spectra of neutral o‐DMTTF molecule. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
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11.
In general, both stoichiometric and catalytic reactions of organometallic complexes involve breaking and forming metal–ligand bonds. Therefore, an evaluation of the thermodynamics of such reactions requires the knowledge of metal–ligand bond energies (BDEs). The homolytic Fe? C bond dissociation energies [i.e., ΔHhomo(Fe? C)s] of 12 para‐substituted benzyldicarbonyl(η5‐cyclopentadienyl)iron, p‐G‐C6H4CH2Fp [1,G = NO2, CN, COMe, CO2Me, CF3, Br, Cl, F, H, Me, MeO, NMe2; Fp = (η5‐C5H5)(CO)2Fe] and 12 para‐substituted α‐cyanobenzyldicarbonyl (η5‐cyclopentadienyl)iron, p‐G‐PANFp [2,PAN = C6H4CH(CN)] were studied using Hartree–Fock (HF) and density functional theory (DFT) methods with large basis sets. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔHhomo(Fe? C)s. The B3LYP method satisfactorily predicts the α and remote substituent effects on ΔHhomo(Fe? C)s [ΔΔHhomo(Fe? C)s]. The fair correlations [r = 0.97 (g, 1), 0.99(g, 2)] of ΔΔHhomo(Fe? C)s of series 1 and 2 with the substituent σ constants imply that the para substituent effects on ΔHhomo(Fe? C)s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. The molecule stabilization effects (MEs) causes that not only the magnitude of ΔΔHhomo(Fe? C)s(1) varies significantly but also the direction changes from S‐pattern to O‐pattern. ΔΔHhomo(Fe? C)s(2) were found to conform to the Capto‐dative Principle. The detailed knowledge of the factors that determine the Fp? C bond strengths would greatly aid in understanding reactivity patterns in many processes. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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13.
Kris Krug Liisa Porra Paola Coan Arie Wallert Joris Dik Andrea Coerdt Alberto Bravin Muthaffar Elyyan Péter Reischig Lukas Helfen Tilo Baumbach 《Journal of synchrotron radiation》2008,15(1):55-61
X‐ray radiography is a common tool in the study of old master paintings. Transmission imaging can visualize hidden paint layers as well as the structure of the panel or canvas. In some medieval altarpieces, relics seem to have been imbedded in the wooden carrier of paintings. These are most probably thin organic fibrous materials such as paper or textile, which in traditional radiography are shadowed by the more absorbing surrounding material. This paper studies the application potential of synchrotron‐based tomographic and laminographic imaging complemented with phase‐contrast imaging for detection of such relics. The techniques are applied to a dummy painting. The results demonstrate that by using these imaging methods it is possible to three‐dimensionally visualize hidden cavities in panels and detect thin fibrous low‐Z materials sandwiched between a high‐Z paint layer and a thick wooden panel. 相似文献
14.
Valery A. Ozeryanskii Ekaterina A. Filatova Alexander F. Pozharskii Dmitrii A. Shevchuk Vladimir I. Sorokin 《Journal of Physical Organic Chemistry》2013,26(6):492-502
Through‐conjugation for a wide range of 1,8‐diamino‐4,5‐dinitronaphthalenes (N‐acylated, N‐alkylated, N,N′‐bridged, N‐heterocyclic, and N‐deprotonated compounds) was for the first time quantified in solution by means of ultraviolet–visible and proton nuclear magnetic resonance spectroscopy and compared with that of the simpler naphthalene and benzene push‐pull systems. Surprisingly, an extent of conjugation in 1,8‐diamino‐4‐nitro‐ and 1,8‐diamino‐4,5‐dinitronaphthalenes measured in dimethyl sulfoxide is commensurable. On the whole, the repulsive peri‐interactions between the amino groups in systems with N‐alkylated and N‐deprotonated amino groups are more favorable for an effective D‐π‐A charge transfer than in N,N′‐bridged compounds (perimidines, 2,3‐dihydroperimidines and perimidin‐2‐ones). The best electron donors from peri‐positions are pyrrolidin‐1‐yl and methylamido groups. The conclusions obtained from solution studies were deepened by solid‐ state X‐ray experiments for a number of push–pull naphthalenes, including 6,7‐dinitroperimidine N‐anion and two representatives of 4,5‐diaminonaphthalene‐1,8‐dicarbaldehydes. In particular, they helped to trace changes in the bond order redistribution and twisting of the naphthalene core. The latter reaches a record value of 27° for 4,5‐dinitro‐1,8‐di(pyrrolidin‐1‐yl)naphthalene. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
15.
Janusz Garecki 《Annalen der Physik》2002,11(6):442-456
We show that gravitational waves which possess a non‐vanishing Riemann tensor Riklm ≠ 0 always carry energy‐momentum and angular momentum. Our proof uses canonical superenergy and supermomentum tensors for the gravitational field. 相似文献
16.
Alina T. Dubis Piotr Stasiewicz Katarzyna Pogorzelec‐Glaser Andrzej Łapiński 《Journal of Physical Organic Chemistry》2015,28(10):652-662
The formation of intramolecular hydrogen bonding by certain N‐substituted 2‐acylpyrroles has been demonstrated by B3LYP/aug‐cc‐pVDZ calculations, the quantum theory of atoms in molecules, and the natural bond orbital method. Total electron energy densities HBCP at the bond critical point of the H?O bond were applied to analyze the strength of these interactions. The relations between quantum theory of atoms in molecules, carbonyl stretching vibrational modes νC = O, and natural bond orbital parameters associated with the formation of the C–H?O interaction have been established. The short contacts were found experimentally in the crystal structure of a new 2‐acylpyrrole derivative 5‐chloro‐2‐oxopentyl‐1‐(5‐chloro‐2‐oxopentyl)pyrrolo‐2‐carboxylate. The influence of 2‐ and N‐substitution of 2‐acylpyrroles on C‐H?O interaction energy is discussed. It was found that the methylene group may act as a proton donor leading to a red‐shift or blue‐shift phenomenon of the νC–H stretching mode. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
17.
Yasuhito Takahashi Takaaki Shishido Kengo Yamamoto Yasunobu Sawaji Jun Nishida Giuseppe Pezzotti 《Journal of Raman spectroscopy : JRS》2015,46(11):1166-1172
Near‐infrared (NIR) Raman microprobe spectroscopy has been applied to the non‐invasive characterization of the biochemical structure of extracellular matrix in articular cartilage, a step forward along the path of in vivo diagnostic application of chondropathy. In most studies handling ex vivo cartilage specimens, formalin fixation or freeze‐thaw treatments have been applied in order to stabilize tissue and cell constituents prior to spectroscopic measurements. However, these pre‐processing manipulations might significantly affect certain target bands of the cartilage spectra, thus introducing biases in the characterizations, and potentially leading to data misinterpretation. In this study, we evaluated how formalin fixing and freeze‐thaw processes affect Raman spectra from human femur cartilage. Healthy cartilage specimens were fixed/stored either in a 10% neutral buffered formalin solution or in a deep freezer set at −80 °C. The results of this study show that formalin fixation significantly affects the NIR Raman spectra of cartilage specimens due to concurrent formalin absorption and water dehydration within both collagen and glycosaminoglycan macromolecules. Water dehydration was also confirmed in the amide I structure in the frozen‐thawed specimen, but to a much lesser extent. Furthermore, soaking the tissues in phosphate‐buffered saline solution minimized the storage‐induced Raman artifacts, but its immersion had limited effectiveness in formalin‐fixed specimens, predominantly due to an overlap of signals from the formalin liquid (i.e. emitting at 1046 and 1492 cm−1). Therefore, to provide a highly accurate biochemical evaluation of extracellular matrix using NIR Raman spectroscopy, freeze‐thaw processes are more suitable for ex vivo samples of human cartilage than formalin fixation. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
18.
铁基超导体的发现开启了探索超导材料的新一轮热潮。最新发现的铁基超导体KxFe2-ySe2有着许多不同寻常的性质。此材料中明显存在相分离,材料中主要的部分是具有反铁磁性质的绝缘相K<sub<2</sub<Fe<sub<4</sub<Se<sub<5</sub<,,超导相只占少量体积。但是超导相在物理上很重要,因为根据理论计算,该材料中不存在空穴型费米面,这样该领域中被广泛接受的S<sup<±</sup<; 配对图像似乎受到挑战。相分离的存在致使此材料中相关研究的难度非常大。该文介绍了此材料中超导相的探索和研究,确认了此材料的超导相是以三维网络状的细丝形态存在,并提出超导的母体相可能是每8个Fe位置有一个Fe空位形成的√8× √10这种有序平行四边形结构,称为K<sub<2</sub<Fe<sub<7</sub<Se<sub<8</sub<相。 相似文献
19.
Kiichirou?Koyasu Wilko?Westh?user Marco?Niemietz Jan?Heinen Gerd?Gantef?r 《Applied Physics A: Materials Science & Processing》2009,96(3):679-684
Using time-resolved photoelectron spectroscopy, the decay channels of AuO2− and Au2O2− following photoexcitation with 3.1-eV photons have been studied. For AuO2−, a state with a rather long lifetime of 30 ps has been identified. Its decay path could not be determined but photodesorption
can be excluded. For Au2O2−, the spectra indicate O2 desorption after 3.1-eV photoexcitation on a time scale of 1 ps. While comparing these results on Au
n
O2− with analogous data on Ag
n
O2− clusters, a discernible pattern emerges: for dissociatively bound O2(AuO2−, Ag3O2−), there are long-living excited states which do not decay by oxygen desorption, while for molecular chemisorption (Au2O2−, Ag2O2−, Ag4O2−, Ag8O2−), the 3.1-eV photoexcitation triggers fast O2 desorption with a high quantum yield. 相似文献
20.
N. A. Kalanda G. G. Gorokh M. V. Yarmolich A. A. Lozovenko E. Yu. Kanyukov 《Physics of the Solid State》2016,58(2):351-359
A method has been developed for fabricating nanoporous matrices based on anodic aluminum oxide for the deposition of ferromagnetic nanoparticles in them. The modes of deposition of strontium ferromolybdate thin films prepared by the ion-plasma method have been worked out, and the magnetic and magnetoresistive properties, structure, and composition of the films have been investigated. It has been revealed that the microstructure and properties of the strontium ferromolybdate films deposited by ionplasma sputtering depend on the deposition rate and the temperature of the substrate. Based on the measurement of the electrical resistivity of nanoheterostructures in a magnetic field, it has been found that the magnetoresistance reaches 14% at T = 15 K and B = 8 T, which is due to the manifestation of tunneling magnetoresistance. 相似文献