共查询到20条相似文献，搜索用时 343 毫秒
1.
The adduct of the hydroxyl radical with oxygen has been studied theoretically, in connection with atmospheric reactions, but its stability and structure remained an open question. Pure rotational spectra of the HOOO and DOOO radicals have now been observed in a supersonic jet by using a Fourier-transform microwave spectrometer with a pulsed discharge nozzle. The molecular constants extracted from 12 rotational transitions with fine and hyperfine splittings support a trans planar molecular structure, in contrast to the cis planar structure predicted by most ab initio calculations. The bond linking the HO and O2 moieties is fairly long (1.688 angstroms) and comparable to the F-O bond in the isoelectronic FOO radical. 相似文献
2.
The Standard Model of particle physics assumes that the so-called fundamental constants are universal and unchanging. Absorption lines arising in molecular clouds along quasar sightlines offer a precise test for variations in the proton-to-electron mass ratio, mu, over cosmological time and distance scales. The inversion transitions of ammonia are particularly sensitive to mu as compared to molecular rotational transitions. Comparing the available ammonia spectra observed toward the quasar B0218+357 with new, high-quality rotational spectra, we present the first detailed measurement of mu with this technique, limiting relative deviations from the laboratory value to |Deltamu/mu| < 1.8 x 10(-6) (95% confidence level) at approximately half the universe's current age-the strongest astrophysical constraint to date. Higher-quality ammonia observations will reduce both the statistical and systematic uncertainties in these observations. 相似文献
3.
MC McCarthy MJ Travers A Kovacs W Chen SE Novick CA Gottlieb P Thaddeus 《Science (New York, N.Y.)》1997,275(5299):518-520
Two cumulene carbenes, H2C5 and H2C6, were detected in a supersonic molecular beam by Fourier transform microwave spectroscopy. Their rotational and leading centrifugal distortion constants were determined with high accuracy, such that the entire radio spectrum can now be calculated. Like the known carbenes H2C3 and H2C4, both molecules have singlet electronic ground states and linear carbon-chain backbones. They can be produced in sufficiently high concentrations in the laboratory that their electronic spectra, expected to lie in the visible, should be readily detectable by laser spectroscopy. The microwave spectra of other, more exotic isomers may be detectable as well. 相似文献
4.
Thioformaldehyde (H(2)CS) has been detected and characterized from its microwave spectrum. Preliminary analysis of rotational transitions for the sulfur-32-containing form of H(2)CS shows this new species to have C(2v) symmetry with rotational constants (in megahertz) of A = 292,729, B = 17,698, and C = 16,652. The possibility of detection of thioformaldehyde in the interstellar medium is discussed, and a table of transitions expected to be of importance for that detection is presented. 相似文献
5.
Even in small molecules, the influence of electronic state on rotational and vibrational product energies is not well understood. Here, we use experiments and theory to address this issue in photodissociation of formaldehyde, H2CO, to the radical products H + HCO. These products result from dissociation from the singlet ground electronic state or the first excited triplet state (T1) of H2CO. Fluorescence spectra reveal a sudden decrease in the HCO rotational energy with increasing photolysis energy accompanied by substantial HCO vibrational excitation. Calculations of the rotational distribution using an ab initio potential energy surface for the T1 state are in very good agreement with experiment and strongly support dominance of the T1 state in the dynamics at the higher photolysis energies. 相似文献
6.
Cruzan JD Braly LB Liu K Brown MG Loeser JG Saykally RJ 《Science (New York, N.Y.)》1996,271(5245):59-62
Measurement of the far-infrared vibration-rotation tunneling spectrum of the perdeuterated water tetramer is described. Precisely determined rotational constants and relative intensity measurements indicate a cyclic quasi-planar minimum energy structure, which is in agreement with recent ab initio calculations. The O-O separation deduced from the data indicates a rapid exponential convergence to the ordered bulk value with increasing cluster size. Observed quantum tunneling splittings are interpreted in terms of hydrogen bond rearrangements connecting two degenerate structures. 相似文献
7.
Peroxy radicals and their derivatives are elusive but important intermediates in a wide range of oxidation processes. We observed pure rotational transitions of the water-hydroperoxy radical complex, H2O-HO2, in a supersonic jet by means of a Fourier transform microwave spectrometer combined with a double-resonance technique. The observed rotational transitions were found to split into two components because of the internal rotation of the water moiety. The molecular constants for the two components were determined precisely, supporting a molecular structure in which HO2 acts as a proton donor to form a nearly planar five-membered ring, and one hydrogen atom of water sticks out from the ring plane. The structure and the spectral splittings due to internal rotation provide information on the nature of the bonding interaction between open- and closed-shell species, and they also provide accurate transition frequencies that are applicable to remote sensing of this complex, which may elucidate its potential roles in atmospheric and combustion chemistry. 相似文献
8.
主要以草地群落的样方调查数据为基础，针对3种不同利用方式下的退化草地群落进行群落结构及多样性的分析，并进行了对比研究。结果表明：尽管禁牧对增加草地植物优势种的重要值起到了一定作用，增加了草地植物群落的密度、盖度等，减少了有毒牧草，但要发展草地畜牧业就不可能一直完全禁牧下去，对比以草定畜与六区轮牧的放牧方式，虽然随着月份变化，以草定畜样地的多样性程度上升，但这种大幅变动有可能是草地群落恢复性较差的表现，而六区轮牧的多样性3种指数的月份变化是有规律性的，相对于以草定畜的草地群落恢复性应该是较好的，可知以六区轮牧对草地植物群落的恢复较为有利。 相似文献
9.
Myoglobin diffusion in bovine heart muscle 总被引：15，自引：0，他引：15
The rotational mobility of myoglobin in situ was determined by proton nuclear magnetic resonance line width measurements of a characteristic myoglobin resonance observed in bovine heart muscle spectra. The protein diffuses intracellularly at nearly half the rate observed in dilute solution. This high mobility allows the oxygenated form of myoglobin to contribute significantly to the overall diffusive flux of oxygen in respiring heart muscle. 相似文献
10.
Pfanstiel JF Champagne BB Majewsi WA Plusquellic DF Pratt DW 《Science (New York, N.Y.)》1989,245(4919):736-738
Band 1 in the jet-cooled one-photon S(1) <-- S(0) fluorescence excitation spectrum of all-trans-1,4-diphenyl-1,3-butadiene has been rotationally resolved with a molecular beam laser spectrometer. Both the orientation of the optical transition moment and the rotational constants of the two vibronic levels have been measured. The molecule shows no evidence of being significantly distorted from a C(24) geometry when it is low in the vibrational manifolds of either of the two electronic states. 相似文献
11.
The laser-induced movement of CO molecules over a platinum surface was followed in real time by means of ultrafast vibrational spectroscopy. Because the CO molecules bound on different surface sites exhibit different C-O stretch vibrational frequencies, the site-to-site hopping, triggered by excitation with a laser pulse, can be determined from subpicosecond changes in the vibrational spectra. The unexpectedly fast motion--characterized by a 500-femtosecond time constant--reveals that a rotational motion of the CO molecules, rather than pure translation, is required for this diffusion process. This conclusion is corroborated by density functional theory calculations. 相似文献
12.
Ultrasonic irradiation of liquids causes acoustic cavitation: the formation, growth, and implosive collapse of bubbles. Bubble collapse during cavitation generates transient hot spots responsible for high-energy chemistry and emission of light. Determination of the temperatures reached in a cavitating bubble has remained a difficult experimental problem. As a spectroscopic probe of the cavitation event, sonoluminescence provides a solution. Sonoluminescence spectra from silicone oil were reported and analyzed. The observed emission came from excited state C(2) (Swan band transitions, d(3)IIg-a(3)II(micro)), which has been modeled with synthetic spectra as a function of rotational and vibrational temperatures. From comparison of synthetic to observed spectra, the effective cavitation temperature was found to be 5075 +/- 156 K. 相似文献
13.
The puzzling mass-independent isotopic enrichment in ozone formation contrasts markedly with the more recently observed large unconventional mass-dependent ratios of the individual ozone formation rate constants in certain systems. An RRKM (Rice, Ramsperger, Kassel, Marcus)-based theory is used to treat both effects. Restrictions of symmetry on how energy is shared among the rotational/vibrational states of the ozone isotopomer, together with an analysis of the competition between the transition states of its two exit channels, permit the calculation of isotope effects consistent with a wide array of experimental results. 相似文献
14.
A quantum statistical treatment of the chemical exchange between molecular eigenstates or conformations revealed previously unsuspected dynamic terms in the spin Hamiltonian operator that describes fast exchange. These terms resulted from the effect of nuclear spin on rotational and vibrational relaxation. With the traditional theory, an interpretation of new carbon-13 nuclear magnetic resonance measurements of the chemical shift of methylcyclohexane in solution showed fast-exchange equilibrium constants that were inconsistent with the slow-exchange free-energy difference and were spread over a range of 30 percent for the various carbon-13 positions. Modeling of the new terms indicated that they have the correct magnitude and temperature dependence to reconcile these inconsistencies. 相似文献
15.
Sinn H Glorieux B Hennet L Alatas A Hu M Alp EE Bermejo FJ Price DL Saboungi ML 《Science (New York, N.Y.)》2003,299(5615):2047-2049
Collective excitations have been observed in liquid aluminum oxide at high temperatures by combining a containerless sample environment with inelastic x-ray scattering. The excitation spectra show a well-defined triplet peak structure at lower wave vectors Q (1 to 6 nanometers-1) and a single quasi-elastic peak at higher Q. The high-Q spectra are well described by kinetic theory. The low-Q spectra require a frequency-dependent viscosity and provide previously unknown experimental constraints on the behavior of liquids at the interface between atomistic and continuum theory. 相似文献
16.
Mayorov AS Elias DC Mucha-Kruczynski M Gorbachev RV Tudorovskiy T Zhukov A Morozov SV Katsnelson MI Fal'ko VI Geim AK Novoselov KS 《Science (New York, N.Y.)》2011,333(6044):860-863
The nematic phase transition in electronic liquids, driven by Coulomb interactions, represents a new class of strongly correlated electronic ground states. We studied suspended samples of bilayer graphene, annealed so that it achieves very high quasiparticle mobilities (greater than 10(6) square centimers per volt-second). Bilayer graphene is a truly two-dimensional material with complex chiral electronic spectra, and the high quality of our samples allowed us to observe strong spectrum reconstructions and electron topological transitions that can be attributed to a nematic phase transition and a decrease in rotational symmetry. These results are especially surprising because no interaction effects have been observed so far in bilayer graphene in the absence of an applied magnetic field. 相似文献
17.
采用荧光猝灭光谱、同步荧光光谱和紫外-可见吸收光谱,研究了白藜芦醇与牛血清白蛋白(BSA)的相互作用。结果表明白藜芦醇对BSA有较强的荧光猝灭作用,荧光猝灭机理属于二者形成复合物所引起的静态猝灭和非辐射能量转移;根据不同温度下防己诺林碱对BSA的荧光猝灭作用,利用Stern-Volmer方程处理实验数据,得到白藜芦醇与BSA之间的结合常数KA为6.11×104(25℃)、4.46×104(35℃)和3.84×104(45℃)。根据F rster非辐射能量转移理论,求出了白藜芦醇与BSA之间的结合距离为2.36 nm(25℃)、2.73 nm(35℃)和2.48 nm(45℃)。通过计算热力学参数,可知该药物与牛血清白蛋白的相互作用是一个吉布斯自由能降低的自发过程,且二者之间的主要作用力类型为疏水作用力,同时用同步荧光光谱探讨了白藜芦醇对BSA构象的影响。 相似文献
18.
Protonated methane, CH5+, has unusual vibrational and rotational behavior because its three nonequivalent equilibrium structures have nearly identical energies and its five protons scramble freely. Although many theoretical papers have been published on the quantum mechanics of the system, a better understanding requires spectral data. A complex, high-resolution infrared spectrum of CH5+ corresponding to the C-H stretching band in the 3.4-micrometer region is reported. Although no detailed assignment of the individual lines was made, comparison with other carbocation spectra strongly suggests that the transitions are due to CH5+. 相似文献
19.
利用紫外光谱和荧光光谱研究二代抗凝杀鼠剂溴敌隆(BRD)与小牛胸腺DNA(ct-DNA)的相互作用.结果表明:ct-DNA可使BRD的紫外吸收光谱发生增色,但试验中没有观察到明显的光谱红移及等吸收点的出现;ct-DNA对BRD的稳态荧光有明显的猝灭作用,属于静态猝灭方式;通过热力学分析判断BRD与ct-DNA之间的相互作用主要是氢键和范德华力作用.吸收光谱、竞争试验、阴离子猝灭试验以及离子强度影响试验一致表明,BRD与ct-DNA之间主要以沟区结合方式发生作用. 相似文献
20.
Pérez C Muckle MT Zaleski DP Seifert NA Temelso B Shields GC Kisiel Z Pate BH 《Science (New York, N.Y.)》2012,336(6083):897-901
Theory predicts the water hexamer to be the smallest water cluster with a three-dimensional hydrogen-bonding network as its minimum energy structure. There are several possible low-energy isomers, and calculations with different methods and basis sets assign them different relative stabilities. Previous experimental work has provided evidence for the cage, book, and cyclic isomers, but no experiment has identified multiple coexisting structures. Here, we report that broadband rotational spectroscopy in a pulsed supersonic expansion unambiguously identifies all three isomers; we determined their oxygen framework structures by means of oxygen-18-substituted water (H(2)(18)O). Relative isomer populations at different expansion conditions establish that the cage isomer is the minimum energy structure. Rotational spectra consistent with predicted heptamer and nonamer structures have also been identified. 相似文献