Desorption of H from Si(111) by resonant excitation of the Si-H vibrational stretch mode

Past efforts to achieve selective bond scission by vibrational excitation have been thwarted by energy thermalization. Here we report resonant photodesorption of hydrogen from a Si(111) surface using tunable infrared radiation. The wavelength dependence of the desorption yield peaks at 0.26 electron volt: the energy of the Si-H vibrational stretch mode. The desorption yield is quadratic in the infrared intensity. A strong H/D isotope effect rules out thermal desorption mechanisms, and electronic effects are not applicable in this low-energy regime. A molecular mechanism accounting for the desorption event remains elusive.     

A new laboratory source of ozone and its potential atmospheric implications

Although 248-nanometer radiation falls 0.12 electron volt short of the energy needed to dissociate O(2) large densities of ozone (O(3)) can be produced from unfocused 248-nanometer KrF excimer laser irradiation of pure O(2). The process is initiated in some undefined manner, possibly through weak two-photon O(2) dissociation, which results in a small amount of O(3) being generated. As soon as any O(3) is present, it strongly absorbs the 248-nanometer radiation and dissociates to vibrationally excited ground state O(2) (among other products), with a quantum yield of 0.1 to 0.15. During the laser pulse, a portion of these molecules absorb a photon and dissociate, which results in the production of three oxygen atoms for one O(3) molecule destroyed. Recombination then converts these atoms to O(3), and thus O(3) production in the system is autocatalytic. A deficiency exists in current models of O(3) photochemistry in the upper stratosphere and mesosphere, in that more O(3) iS found than can be explained. A detailed analysis of the system as it applies to the upper atmosphere is not yet possible, but with reasonable assumptions about O(2) vibrational distributions resulting from O(3) photodissociation and about relaxation rates of vibrationally excited O(2) a case can be made for the importance of incuding this mechanism in the models.     

Signatures of H2CO photodissociation from two electronic states

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.     

A linear, O-coordinated eta1-CO2 bound to uranium

The electron-rich, six-coordinate tris-aryloxide uranium(III) complex [((AdArO)3tacn)U(III)] [where (AdArOH)3tacn = 1,4,7-tris(3-adamantyl-5-tert-butyl-2-hydroxybenzyl)1,4,7-triazacyclononane] reacts rapidly with CO2 to yield [((AdArO)3tacn)U(IV)(CO2)], a complex in which the CO(2) ligand is linearly coordinated to the metal through its oxygen atom (eta1-OCO). The latter complex has been crystallographically and spectroscopically characterized. The inequivalent O-C-O bond lengths [1.122 angstroms (A) for the O-C bond adjacent to uranium and 1.277 A for the other], considered together with magnetization data and electronic and vibrational spectra, support the following bonding model: U(IV)=O=C*-O- <--> U(IV)-OC-O-. In these charge-separated resonance structures, the uranium center is oxidized to uranium(IV) and the CO2 ligand reduced by one electron.     

Experimental test of self-shielding in vacuum ultraviolet photodissociation of CO

Self-shielding of carbon monoxide (CO) within the nebular disk has been proposed as the source of isotopically anomalous oxygen in the solar reservoir and the source of meteoritic oxygen isotopic compositions. A series of CO photodissociation experiments at the Advanced Light Source show that vacuum ultraviolet (VUV) photodissociation of CO produces large wavelength-dependent isotopic fractionation. An anomalously enriched atomic oxygen reservoir can thus be generated through CO photodissociation without self-shielding. In the presence of optical self-shielding of VUV light, the fractionation associated with CO dissociation dominates over self-shielding. These results indicate the potential role of photochemistry in early solar system formation and may help in the understanding of oxygen isotopic variations in Genesis solar-wind samples.     

UV Spectrum and Proposed Role of Diethylberyllium in a 7Li-7Be Solar Neutrino Experiment

Although measurement of the solar neutrino flux via the (7)Li(v(e),e(-))(7)Be reaction was proposed many years ago, no experiment has been implemented since it has been difficult to identify a sensitive (7)Be detection technique. Here it is proposed that the (7)Be atom be incorporated into a volatile molecule, placed in a buffer-gas-filled cell, and then extracted by photodissociation; after excitation by a tunable laser, bursts of photons would be detected. The absorption spectrum of the molecular candidate diethylberyllium has been measured between 186 and 270 nanometers in a spectrophotometer to determine the required photodissociation laser wavelength and intensity.     

Picosecond time-resolved resonance Raman studies of hemoglobin: implications for reactivity

Picosecond time-resolved Raman spectra of hemoglobin generated with blue pulses (20 to 30 picoseconds) that were resonant with the Soret band and of sufficient intensity to completely photodissociate the starting liganded sample are reported. For both R- and T-state liganded hemoglobins, the peak frequencies in the spectrum of the deoxy transient were the same at approximately 25 picoseconds as those observed at 10 nanoseconds subsequent to photodissociation. In particular, the large R-T differences in the frequency of the stretching mode for the iron-proximal histidine bond (VFe-His) detected in previously reported nanosecond-resolved spectra were also evident in the picosecond-resolved spectra. The implications of this finding with respect to the distribution of strain energy in the liganded protein and the origin of the time course for geminate recombination are discussed. On the basis of these results, a microscopic model is proposed in which delocalization of strain energy is strongly coupled to the coordinate of the iron. The model is used to explain the origin of the R-T differences in the rates of ligand dissociation.     

Stable Isotope Studies of Crop Carbon and Water Relations： A Review

Crop carbon and water relations research is important in the studies of water saving agriculture, breeding program, and energy and material cycles in soil plant atmosphere continuum （SPAC）. The purpose of this paper is to review the current state of knowledge on stable isotopes of carbon, oxygen, and hydrogen in the research of crop carbon and water relations, such as carbon isotope discrimination （△^13C） during carbon fixation process by photosynthesis, application of △^13C in crop water use efficiency （WUE） and breeding programs, oxygen isotope enrichment during leaf water transpiration, CO2 fixation by photosynthesis and release by respiration, application of hydrogen isotope composition （619） and oxygen isotope composition （6180） for determination of water source used by a crop, stable isotope coupling Keeling plot for investigating the carbon and water flux in ecosystem, energy and material cycle in SPAC and correlative integrative models on stable isotope. These aspects contain most of the stable isotope researches on crop carbon and water relations which have been widely explored internationally while less referred in China. Based on the reviewed literatures, some needs for future research are suggested.     

Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.     

Carbon-13/carbon-12 isotope fractionation of organic matter associated with uranium ores induced by alpha irradiation

Analyses of stable carbon isotopes from two sample suites from sandstone uranium (tabular) ores show interesting variations. Organic carbon associated with high-grade uranium ore is heavy (delta(13)C = -16.9 to -19.6 per mil, where delta(13)C = (13)C/(12)C relative to the Pee Dee belemnite standard) relative to the adjacent lower-grade samples (-22.7 to -26.4 per mil). It is suggested that the heavy isotopic values for the are samples are related to a radiation and chemical isotope effect that has occurred mainly because of an alpha-radiation dose of 10(11) rads.     

The little ice age as recorded in the stratigraphy of the tropical quelccaya ice cap

The analyses of two ice cores from a southern tropical ice cap provide a record of climatic conditions over 1000 years for a region where other proxy records are nearly absent. Annual variations in visible dust layers, oxygen isotopes, microparticle concentrations, conductivity, and identification of the historical (A.D. 1600) Huaynaputina ash permit accurate dating and time-scale verification. The fact that the Little Ice Age (about A.D. 1500 to 1900) stands out as a significant climatic event in the oxygen isotope and electrical conductivity records confirms the worldwide character of this event.     

How do small water clusters bind an excess electron?

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-].     

The "Ozone Deficit" Problem: O2(X, v ge 26) + O(3P) from 226-nm Ozone Photodissociation

Highly vibrationally excited O(2)(X(3)sigmag(-), v >/= 26) has been observed from the photodissociation of ozone (O(3)), and the quantum yield for this reaction has been determined for excitation at 226 nanometers. This observation may help to address the "ozone deficit" problem, or why the previously predicted stratospheric O(3) concentration is less than that observed. Recent kinetic studies have suggested that O(2)(X(3)sigmag(-), v >/= 26) can react rapidly with O(2) to form O(3) + O and have led to speculation that, if produced in the photodissociation of O(3), this species might be involved in resolving the discrepancy. The sequence O(3) + hv --> O(2)(X(3)sigmag(-), v >/= 26) + O; O(2)(X(3)sigmag(-), v >/= 26) + O(2) --> O(3) + O (where hv is a photon) would be an autocatalytic mechanism for production of odd oxygen. A two-dimensional atmospheric model has been used to evaluate the importance of this new mechanism. The new mechanism can completely account for the tropical O(3) deficit at an altitude of 43 kilometers, but it does not completely account for the deficit at higher altitudes. The mechanism also provides for isotopic fractionation and may contribute to an explanation for the anomalously high concentration of heavy O(3) in the stratosphere.     

Delocalization of protons in liquid water

We find that the vibrational potential of the O-H stretch vibrations of liquid water shows extreme anharmonicity that arises from the O-H O hydrogen bond interaction. We observe that already in the second excited state of the O-H stretch vibration, the hydrogen atom becomes delocalized between the oxygen atoms of two neighboring water molecules. The energy required for this delocalization is unexpectedly low and corresponds to less than 20% of the dissociation energy of the O-H bond of the water molecule in the gas phase.     

稳定同位素在植物水分来源及利用效率研究中的应用

介绍了稳定氢、氧、碳同位素技术在定量区分植物水分来源及利用效率研究中的应用。以往大量研究结果表明,由于植物根系在吸收水分过程中没有发生同位素分馏,所以通过比较和分析植物木质部水分及其可利用水源的氢氧同位素δ值,就可以定量判断植物的水源;植物在光合作用过程中会产生碳同位素的分馏,从而使得植物叶片中的碳同位素组成能够成为指示植物水分利用效率的一个间接指标,是目前研究植物叶片长期水分利用效率的最佳方法;稳定同位素技术作为安全的示踪剂,有助于人类了解植物的生理生态功能,随着该技术的不断完善和研究的不断深入,同位素技术将会在生态学研究的许多领域得到广泛的应用。     

电子相关效应和相对论效应对CuIn分子基态X1∑+平衡几何构型和稳定性的修正

使用相对论与非相对论赝势,在HF、B3LYP水平上详细研究了电子相关效应和相,謦誉謦尊CuIn分子平衡几何构型和能量的影响。结果显示,电子相关效应缩短核间距,提高振动频率,降低能量;相对论效应加强了它的强度,使CuIn分子更加稳定。同时,在B3LYP水平上采用相对论有效核芯势（RCEP）进行能量扫描得型了CuIn分子势能曲线,给出CuIn分子的力参数和光谱数据。计算结果显示,得到的Culn分子基态平衡几何、振动频率、解离能等与可得到的试验结果吻合。     

Oxygen isotopes and the moon-forming giant impact

We have determined the abundances of 16O, 17O, and 18O in 31 lunar samples from Apollo missions 11, 12, 15, 16, and 17 using a high-precision laser fluorination technique. All oxygen isotope compositions plot within +/-0.016 per mil (2 standard deviations) on a single mass-dependent fractionation line that is identical to the terrestrial fractionation line within uncertainties. This observation is consistent with the Giant Impact model, provided that the proto-Earth and the smaller impactor planet (named Theia) formed from an identical mix of components. The similarity between the proto-Earth and Theia is consistent with formation at about the same heliocentric distance. The three oxygen isotopes (delta17O) provide no evidence that isotopic heterogeneity on the Moon was created by lunar impacts.     

Stable Isotope Technique—An Advanced Technology in Ascertaining Plant-Water Relations

介绍了稳定同位素的一些关键术语和相关标准,探讨了研究植物水分关系中 C、H、O三种稳定同位素的确定及其同位素效应,同时主要从植物水分来源、水分利用效率、根系吸收水分最活跃区域、植物群落内不同物种水资源利用差异等几个方面阐述了稳定同位素先进技术的应用进展,最后指出稳定同位素技术在植物水分关系研究中存在的问题。旨在此文能起到抛砖引玉的作用,以此推动稳定同位素技术在我国植物水分利用研究甚至整个生态学领域研究中的可持续发展。     

Ultrafast dynamics of solute-solvent complexation observed at thermal equilibrium in real time

In general, the formation and dissociation of solute-solvent complexes have been too rapid to measure without disturbing the thermal equilibrium. We were able to do so with the use of two-dimensional infrared vibrational echo spectroscopy, an ultrafast vibrational analog of two-dimensional nuclear magnetic resonance spectroscopy. The equilibrium dynamics of phenol complexation to benzene in a benzene-carbon tetrachloride solvent mixture were measured in real time by the appearance of off-diagonal peaks in the two-dimensional vibrational echo spectrum of the phenol hydroxyl stretch. The dissociation time constant tau(d) for the phenol-benzene complex was 8 picoseconds. Adding two electron-donating methyl groups to the benzene nearly tripled the value of tau(d) and stabilized the complex, whereas bromobenzene, with an electron-withdrawing bromo group, formed a slightly weaker complex with a slightly lower tau(d). The spectroscopic method holds promise for studying a wide variety of other fast chemical exchange processes.     

Oxygen and carbon isotopic growth record in a reef coral from the Florida keys and a deep-sea coral from blake plateau

Carbon and oxygen isotope analysis through a 30-year (1944 to 1974) growth of Montastrea annularis from Hen and Chickens Reef (Florida Keys) shows a strong yearly variation in the abundances of both carbon-13 and oxygen-18 and a broad inverse relationship between the two isotopes. Normal annual dense bands are formed during the summer and are characterized by heavy carbon and light oxygen. "Stress bands" are formed during particularly severe winters and are characterized by heavy carbon and heavy oxygen. The isotopic effect of Zooxanthellae metabolism dominates the temperature effect on the oxygen-18/oxygen-16 ratio. The isotopic results on the deep-sea solitary coral Bathypsammia tintinnabulum, where Zooxanthellae are nonexistent, indicates that the abundance of the heavy isotopes carbon-13 and oxygen-18 is inversely related to the growth rate, with both carbon and oxygen approaching equilibrium values with increasing skeletal age.