共查询到20条相似文献，搜索用时 328 毫秒
1.
Chemical dynamics trajectory simulations were used to study the atomic-level mechanisms of the OH- + CH3F --> CH3OH + F- SN2 nucleophilic substitution reaction. The reaction dynamics, from the [OH...CH3...F]- central barrier to the reaction products, are simulated by ab initio direct dynamics. The reaction's potential energy surface has a deep minimum in the product exit channel arising from the CH3OH...F- hydrogen-bonded complex. Statistical theories of unimolecular reaction rates assume that the reactive system becomes trapped in this minimum and forms an intermediate, with random redistribution of its vibrational energy, but the majority of the trajectories (90%) avoided this potential energy minimum and instead dissociated directly to products. This finding is discussed in terms of intramolecular vibrational energy redistribution (IVR) and the relation between IVR and molecular structure. The finding of this study may be applicable to other reactive systems where there is a hierarchy of time scales for intramolecular motions and thus inefficient IVR. 相似文献
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The quantum solid para-hydrogen (p-H2) has recently proven useful in matrix isolation spectroscopy. Spectral lines of compounds embedded in this host are unusually narrow, and several species have been reported to rotate in p-H2. We found that a p-H2 matrix inhibits rotation of isolated methanol (CH3OH) but still allows internal rotation about the C-O bond, with splittings of the E/A torsional doublet in internal rotation-coupled vibrational modes that are qualitatively consistent with those for CH3OH in the gaseous phase. This simplified high-resolution spectrum further revealed the slow conversion of nuclear spin symmetry from species E to species A in the host matrix, offering potential insight into nuclear spin conversion in astrophysical sources. 相似文献
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Time-resolved sum-frequency vibrational spectroscopy permits the study of hitherto neglected ultrafast vibrational dynamics of neat water interfaces. Measurements on interfacial bonded OH stretch modes revealed relaxation behavior on sub-picosecond time scales in close resemblance to that of bulk water. Vibrational excitation is followed by spectral diffusion, vibrational relaxation, and thermalization in the hydrogen-bonding network. Dephasing of the excitation occurs in 相似文献
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Hammer NI Shin JW Headrick JM Diken EG Roscioli JR Weddle GH Johnson MA 《Science (New York, N.Y.)》2004,306(5696):675-679
The arrangement of water molecules around a hydrated electron has eluded explanation for more than 40 years. Here we report sharp vibrational bands for small gas-phase water cluster anions, (H2O)(4-6)- and (D2O)(4-6)-. Analysis of these bands reveals a detailed picture of the diffuse electron-binding site. The electron is closely associated with a single water molecule attached to the supporting network through a double H-bond acceptor motif. The local OH stretching bands of this molecule are dramatically distorted in the pentamer and smaller clusters because the excited vibrational levels are strongly coupled to the electron continuum. The vibration-to-electronic energy transfer rates, as revealed by line shape analysis, are mode-specific and remarkably fast, with the symmetric stretching mode surviving for less than 10 vibrational periods [50 fs in (H2O)4-]. 相似文献
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Mikosch J Trippel S Eichhorn C Otto R Lourderaj U Zhang JX Hase WL Weidemüller M Wester R 《Science (New York, N.Y.)》2008,319(5860):183-186
Anion-molecule nucleophilic substitution (S(N)2) reactions are known for their rich reaction dynamics, caused by a complex potential energy surface with a submerged barrier and by weak coupling of the relevant rotational-vibrational quantum states. The dynamics of the S(N)2 reaction of Cl- + CH3I were uncovered in detail by using crossed molecular beam imaging. As a function of the collision energy, the transition from a complex-mediated reaction mechanism to direct backward scattering of the I- product was observed experimentally. Chemical dynamics calculations were performed that explain the observed energy transfer and reveal an indirect roundabout reaction mechanism involving CH3 rotation. 相似文献
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Prinn RG Huang J Weiss RF Cunnold DM Fraser PJ Simmonds PG McCulloch A Harth C Salameh P O'Doherty S Wang RH Porter L Miller BR 《Science (New York, N.Y.)》2001,292(5523):1882-1888
The hydroxyl radical (OH) is the dominant oxidizing chemical in the atmosphere. It destroys most air pollutants and many gases involved in ozone depletion and the greenhouse effect. Global measurements of 1,1,1-trichloroethane (CH3CCl3, methyl chloroform) provide an accurate method for determining the global and hemispheric behavior of OH. Measurements show that CH3CCl3 levels rose steadily from 1978 to reach a maximum in 1992 and then decreased rapidly to levels in 2000 that were lower than the levels when measurements began in 1978. Analysis of these observations shows that global OH levels were growing between 1978 and 1988, but the growth rate was decreasing at a rate of 0.23 +/- 0.18% year(-2), so that OH levels began declining after 1988. Overall, the global average OH trend between 1978 and 2000 was -0.64 +/- 0.60% year(-1). These variations imply important and unexpected gaps in current understanding of the capability of the atmosphere to cleanse itself. 相似文献
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The coupling of electron and nuclear motions in ultrafast charge transfer at molecule-semiconductor interfaces is central to many phenomena, including catalysis, photocatalysis, and molecular electronics. By using femtosecond laser excitation, we transferred electrons from a rutile titanium dioxide (110) surface into a CH3OH overlayer state that is 2.3 +/- 0.2 electron volts above the Fermi level. The redistributed charge was stabilized within 30 femtoseconds by the inertial motion of substrate ions (polaron formation) and, more slowly, by adsorbate molecules (solvation). According to a pronounced deuterium isotope effect (CH3OD), this motion of heavy atoms transforms the reverse charge transfer from a purely electronic process (nonadiabatic) to a correlated response of electrons and protons. 相似文献
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Shin JW Hammer NI Diken EG Johnson MA Walters RS Jaeger TD Duncan MA Christie RA Jordan KD 《Science (New York, N.Y.)》2004,304(5674):1137-1140
We report the OH stretching vibrational spectra of size-selected H+(H2O)n clusters through the region of the pronounced "magic number" at n = 21 in the cluster distribution. Sharp features are observed in the spectra and assigned to excitation of the dangling OH groups throughout the size range 6 相似文献
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In a suspension of reverse micelles, in which the surfactant sodium dioctyl sulfosuccinate (AOT) separates a water nanodroplet from a bulk nonpolar CCl4 phase, ultrafast vibrational spectroscopy was used to study vibrational energy transfer from the nanodroplet through the AOT interfacial monolayer to the surrounding CCl4. Most of the vibrational energy from the nanodroplet was transferred to the polar AOT head group within 1.8 picoseconds and then out to the CCl4 within 10 picoseconds. Vibrational energy pumped directly into the AOT tail resulted in a slower 20- to 40-picosecond transfer of energy to the CCl4. 相似文献
10.
郎秀峰 《河北农业技术师范学院学报》2014,(4):45-50
基于第一性原理计算,详细研究了完美的金红石型TiO2（110）面上CH3 OH转化为HCOOCH3的氧化机制.计算所得的基元反应的能垒证实了CH3 OH在TiO2 （110）表面上经过脱氢和耦合反应生成了中间物CH3OC（=O） H2,然后经过脱氢生成了最终的产物HCOOCH3. 相似文献
11.
Montzka SA Krol M Dlugokencky E Hall B Jöckel P Lelieveld J 《Science (New York, N.Y.)》2011,331(6013):67-69
The oxidizing capacity of the global atmosphere is largely determined by hydroxyl (OH) radicals and is diagnosed by analyzing methyl chloroform (CH(3)CCl(3)) measurements. Previously, large year-to-year changes in global mean OH concentrations have been inferred from such measurements, suggesting that the atmospheric oxidizing capacity is sensitive to perturbations by widespread air pollution and natural influences. We show how the interannual variability in OH has been more precisely estimated from CH(3)CCl(3) measurements since 1998, when atmospheric gradients of CH(3)CCl(3) had diminished as a result of the Montreal Protocol. We infer a small interannual OH variability as a result, indicating that global OH is generally well buffered against perturbations. This small variability is consistent with measurements of methane and other trace gases oxidized primarily by OH, as well as global photochemical model calculations. 相似文献
12.
Many properties of chemical reactions are determined by the transition state connecting reactant and product, yet it is difficult to directly obtain any information about these short-lived structures in liquids. We show that two-dimensional infrared (2D-IR) spectroscopy can provide direct information about transition states by tracking the transformation of vibrational modes as a molecule crossed a transition state. We successfully monitored a simple chemical reaction, the fluxional rearrangement of Fe(CO)5, in which the exchange of axial and equatorial CO ligands causes an exchange of vibrational energy between the normal modes of the molecule. This energy transfer provides direct evidence regarding the time scale, transition state, and mechanism of the reaction. 相似文献
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8种新疆产干果的红外光谱特征研究 总被引：1，自引：0，他引：1
分析了新疆产8种干果的红外光谱特征。这8种干果可分为两类，其红外图谱在官能团区有很大差异。巴旦木、核桃仁、花生仁、带壳杏仁富含蛋白质和脂类物质，红外图谱显示出在2914，2847cm^-1附近的CH伸缩振动和1742cm^-1附近的C=O伸缩振动；枸杞子、红枣、葡萄干和无花果干富含多糖、蛋白类物质，其红外图谱显示出在3370cm^-1附近的OH变形振动、NH伸缩振动和2920cm^-1附近的CH伸缩振动。 相似文献
16.
Talukdar RK Mellouki A Schmoltner AM Watson T Montzka S Ravishankara AR 《Science (New York, N.Y.)》1992,257(5067):227-230
The rate coefficients for the reaction of hydroxyl (OH) radicals with methyl chloroform (CH(3)CCI(3)) were measured between 243 and 379 kelvin with the pulsed photolysis-laserinduced fluorescence method. The measured rate coefficients at 298 and 277 kelvin were approximately 20 and approximately 15%, respectively, lower than earlier values. These results will increase the tropospheric OH concentrations derived from the CH(3)CCI(3) budget analysis by approximately 15%. The predicted atmospheric lifetimes of species whose main loss process is the reaction with OH in the troposphere will be lowered by 15% with consequent changes in their budgets, global warming potentials, and ozone depletion potentials. 相似文献
17.
By using laser methods to prepare specific quantum states of gas-phase nitric oxide molecules, we examined the role of vibrational motion in electron transfer to a molecule from a metal surface free from the complicating influence of solvation effects. The signature of the electron transfer process is a highly efficient multiquantum vibrational relaxation event, where the nitrogen oxide loses hundreds of kilojoules per mole of energy on a subpicosecond time scale. These results cannot be explained simply on the basis of Franck-Condon factors. The large-amplitude vibrational motion associated with molecules in high vibrational states strongly modulates the energetic driving force of the electron transfer reaction. These results show the importance of molecular vibration in promoting electron transfer reactions, a class of chemistry important to molecular electronics devices, solar energy conversion, and many biological processes. 相似文献
18.
Because of its high resistivity and subsequent low electroactivity, sulfur is not normally considered a room-temperature battery cathode. An elemental sulfur cathode has been made with a measured capacity of over 900 ampere.hours per kilogram, more than 90 percent of the theoretical storage capacity of solid sulfur at room temperature, accessed by means of a lightweight, highly conductive, aqueous polysulfide interface through the electrocatalyzed reaction S + H(2)O + 2e(-) --> HS(-) + OH(-). This solid sulfur cathode was first used in a battery with an aluminum anode for an overall discharge reaction 2Al + 3S + 3OH(-) + 3H(2)O --> 2Al(OH)(3) + 3HS(-), giving a cell potential of 1.3 volts. The theoretical specific energy of the aluminum-sulfur battery (based on potassium salts) is 910 watt.hours per kilogram with an experimental specific energy of up to 220 watt.hours per kilogram. 相似文献
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有机锡对海洋环境有着很大的破坏作用,为此以一甲基氯化锡(CH3SnCl3)和二甲基氯化锡((CH3)2SnCl2)为代表,研究了不同浓度有机锡对斜生栅藻(Scenedesmus obliguus)的毒性影响,并且对两种有机锡的毒性进行了对比试验.结果表明,一甲基氯化锡和二甲基氯化锡对斜生栅藻的生长均有一定抑制作用,且二甲基氯化锡的毒性大于一甲基氯化锡.当有机锡浓度为200 μg·L-1时,对藻细胞的生长抑制达到20.4%;随着有机锡浓度的增加,抑制效应增大. 相似文献