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51.
报道了3-苯基-1-丁炔-3-醇的常规电子轰击质谱(EIMS)。利用碰撞诱导解离(CID)技术研究了质谱碎裂过程中产生的[C8H7]^+的气相离子结构。同时, 氘代同位素交换、亚稳(MI)和CID实验进一步证实了m/z 103离子的形成并不是分子离子的质谱碎裂中顺次失去甲基自由基和中性CO分子的直接氢迁移的协同反应, 而是在失去CO分子前后发生了二次质子迁移反应的逐步过程。在此基础上提出了一种独特的双分子质子键合复合物中间体的碎裂机理。 相似文献
52.
Garth J Simpson 《Chemphyschem》2004,5(9):1301-1310
Recent observations of remarkably large chiroptical effects in second-harmonic generation (SHG) and sum-frequency generation (SFG) measurements suggest exciting possibilities for the development of new chiral-specific spectroscopies and novel chiral materials for nonlinear optics. Several fundamental studies designed to elucidate the molecular and macromolecular origins of the chiral responses are reviewed to provide a framework for development of this emerging field. In general, the chiral activity in SHG and SFG has the potential to arise from complex interactions between hosts of different competing effects. Fortunately, relatively simple electric dipole-allowed mechanisms routinely dominate the nonlinear optical chiral activities of most practical systemsexpressions can often be generated to link the. This substantial reduction in complexity allows for the development of simple models connecting the macroscopic nonlinear optical response to intuitive molecular and supramolecular properties. 相似文献
53.
A recently characterized oviposition-deterring pheromone (ODP, structure 1) of the European cherry fruit fly was used as a test case for probing the potential of tandem mass spectrometry (MS/MS) in structure elucidation as a stand-alone technique. The glycolipid-taurinate 1 was subjected to MS/MS analyses under a variety of conditions with and without preceding chemical degradation. Acidic methanolysis of 1 and subsequent in-batch derivatization (trideuterioacetylation) yielded methyl 2,3,4,6-tetrakis-O-trideuterioacetyl-glucopyranoside (2), methyl 8,15-bis-trideuterioacetoxy-palmitate (3), and taurine (4) as suitable target compounds for direct mixture analysis.Low energy collision induced dissociation (CID) on selected precursor ions (MS/MS on [M + H – CH3OH]+ and [M + H]+ produced by fast atom bombardment (FAB)) allowed direct identification of 2 and 4, respectively, by comparison with appropriate reference ions. In the case of 3, low energy CID (desorption chemical ionization (DCI) instead of FAB, MS/MS on [M + H]+) permitted deduction of gross molecular structure, but failed to provide positional detail. In sharp contrast,high energy CID of trideuterioacetylated intact 1 (FAB-MS/MS on [M – H]– ions of la) clearly revealed a linear 8,15-hydroxylated palmitic acid backbone. Less certain was assignment of 15-O-glucosylation by this approach. 相似文献
54.
Sh. Sh. Nabiev I. I. Ostroukhova N. V. Revina L. P. Sukhanov 《Russian Chemical Bulletin》1998,47(3):417-422
The Raman spectra of ClOF2
+ cation in solutions of anhydrous HF were studied. In the ClOF2
+HF2
− and ClOF2
+BF4
−−HF systems, this cation exists as a pyramidal structure (C
s
symmetry), while in the ClOF2
+AuF6
−−HF system, it exists as a planar structure (C
2v
symmetry). Based on nonempirical calculations by the Hartree-Fock-Roothaan method, an explanation for the dependence of the
structure of the ClOF2
+ cation on the nature of the anion was proposed. For the Cl−O bond vibrations, the correlation functions of vibrational and
rotational relaxations were calculated, and the characteristic times of these processes were determined. The main contribution
to the formation of the band contours corresponding to the above-mentioned modes is made by the vibrational dephasing.
Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 432–437, March, 1998. 相似文献
55.
P. Goy 《International Journal of Infrared and Millimeter Waves》1982,3(2):221-234
This paper describes experimental results obtained with a packaged GaAs Schottky barrier diode in contact with a coaxial connector and placed across waveguides for bands Ka, V, E, W or F. Among the microwave sources used for calibration were 9 carcinotrons in the frequency interval 51–490 GHz. As soon as the frequency F is above the waveguide cut-off frequency, the different characteristics do not depend critically on the waveguide size for V, E, W and F bands. The video detection sensitivity, of several 100 mV/mW at 50 GHz and below, decreases as F–4 in the range 51–500 GHz. Coupling an X-band centimeter frequency via the coaxial connector and a millimeter frequency via the waveguide permits harmonic mixing in the diode. Between 36 and 490 GHz, the harmonic mixing number varies from 3 up to the very large value 40 with conversion losses from 18 to 88 dB. The minimum detectable signal in the 100 kHz band can be as low as –90 dBm at 80 GHz. A noticeable millimeter power is available at the waveguide output from injected centimeter power by harmonic generation. Starting for instance with 100 mW around 11.5 GHz, we have measured 0.1 mW at 80 GHz and 0.1 W at 230 GHz. To illustrate the possibility of creating usable millimeter and submillimeter wave without heavy equipment (such as carcinotrons or millimeter klystron) we report spectroscopic experiments in Rydberg atoms. Resonances have been observed up to 340 GHz by harmonic generation (28th harmonic) from an X-band klystron). 相似文献
56.
Chemical mass shifts were measured in a Paul ion trap operated in the mass-selective instability scan with resonance ejection using a custom-built instrument. These shifts, which can be as much as 2%, decrease with increasing endcap electrode separation owing to changes in the higher order contributions to the electric field. They also decrease with decreasing helium buffer gas pressure. Both of these effects are analogous to those found with boundary ejection. This suggests that the previously proposed chemical mass shift mechanism based on compound-dependent collisional modification of the ejection delay produced by field faults near the endcap electrode apertures holds true also for resonance ejection. The influence of the resonance frequency on chemical mass shifts was also investigated and it is shown that at certain working points (values of the Mathieu parameter q(z) and a(z)) non-linear resonances greatly reduce the ejection delay for all ions, regardless of their chemical structures, and thus reduce the magnitude of the chemical mass shift. Energetic collisions leading to dissociation can take place at an earlier stage during the ejection process in the mass analysis scan when using resonance ejection compared with boundary ejection. This leads to even larger chemical mass shifts of fragile ions in resonance ejection. Increasing the resonance voltage amplitude can enhance this effect. The chemical mass shifts of fragile ions increase with increase in the resonance voltage amplitude, whereas negligible changes occur for structurally stable ions. 相似文献
57.
使用PSD作为大口径光学元件表面加工质量的评价参数,针对不同的波前调制进行了初步的模拟计算,得到了不同调制频率和不同调制深度情况下的PSD曲线变化情况。当调制频率不同时,PSD曲线的突变部分会发生相应的频移,调制频率高则突变发生在空间频率较高的频段,同时PSD峰值不变。相对应调制深度不同时,PSD曲线的突变部份峰值发生变化,调制深度大则峰值大,与此同时峰值出现的位置不会发生变化。计算和分析结果表明PSD分析结果能够在频率域反应出元件表面受到的不同程度的调制信息。 相似文献
58.
59.
Houde Han Zhongyi Huang 《计算数学(英文版)》2008,26(5):728-739
In this paper, we propose a tailored-finite-point method for the numerical simulation of the Helmholtz equation with high wave numbers in heterogeneous medium. Our finite point method has been tailored to some particular properties of the problem, which allows us to obtain approximate solutions with the same behaviors as that of the exact solution very naturally. Especially, when the coefficients are piecewise constant, we can get the exact solution with only one point in each subdomain. Our finite-point method has uniformly convergent rate with respect to wave number k in L^2-norm. 相似文献
60.
Sarvesh Kumar Jos Romero Michael Probst Thana Maihom Gustavo García Paulo Limo-Vieira 《Molecules (Basel, Switzerland)》2022,27(15)
The geometrical effect of chlorine atom positions in polyatomic molecules after capturing a low-energy electron is shown to be a prevalent mechanism yielding Cl2−. In this work, we investigated hexachlorobenzene reduction in electron transfer experiments to determine the role of chlorine atom positions around the aromatic ring, and compared our results with those using ortho-, meta- and para-dichlorobenzene molecules. This was achieved by combining gas-phase experiments to determine the reaction threshold by means of mass spectrometry together with quantum chemical calculations. We also observed that Cl2− formation can only occur in 1,2-C6H4Cl2, where the two closest C–Cl bonds are cleaved while the chlorine atoms are brought together within the ring framework due to excess energy dissipation. These results show that a strong coupling between electronic and C–Cl bending motion is responsible for a positional isomeric effect, where molecular recognition is a determining factor in chlorine anion formation. 相似文献