中能核反应中的统计发射过程及核温度参量

在过去的几年里，利用兰州重离子加速器（HIRFL）提供的束流，以及在OUVERTURE合作研究中，利用意大利国家核物理研究院南方实验室（INFN-LNS）超导回旋提供的束流，进行了多次中能区重离子核反应实验研究工作。如，最初的46.7MeV/u ~(12)C+~(58)Ni，~(115)In，~(197)Au的实验及30MeV/u ~(40)Ar+~(58)Ni，~(64)Ni~(115)In和30MeV/u Ni轰击Ni，Au，Al在MULTICS+MEDEA：4π装置上进行的实验工作。此外，本人还从事过一些理论研究工作，包括多粒子散射形式理论和相关数学物理问题研究，量子分子动力学和量子统计模型计算。本文是从事这些核物理研究工作的积累，主要侧重于实验结果的物理内容分析，而不强调实验技术，数据处理的技巧。主要的物理内容有以下几个方面：1.对于利用双同位素产额比提取同位素核温度的方法进行研究推广，使得对于实验中碰到的仅有部分能谱可以实现很好同位素分辩的情况，即使不能得到总的同位素产额，仅仅通过一段能区的同位素产额也可提取核温度。用于具体的实验研究工作中后，对于46.7MeV/u ~(12)C+~(58)Ni，~(115)In，~(197)Au核反应过程，同一体系利用这种方法得到的同位素核温度和利用粒子非稳态布居提取的核温度一致。2.围绕核反应过程中核温度的参量的提取，对于双同位素产额比与核温度的刻度关系进行了分析研究，通过计算考虑中等质量碎片（IMF）内部激发能后的内部配分函数表明，中等质量碎片的内部激发对刻度关系有重要影响。零阶近似下区域密度近似的结果和Gemini模拟计算的结果反映了相同的情况。3.研究核反应机制，多个粒子散射的形式理论的必需的，对于两体散射，其形式理论已经比较成熟，但是对于多个粒子散射问题出现的严重的困难是多体Lippmann-Schwinger方程无唯一收敛的解。作为一种探索性的研究工作，开展了多体散射理论研究工作，发展了一些具有普遍意义的数学物理方法。在本项研究工作中，通过能基础数学中的约当引理的推广，发现一个特例：对非连接图，Lippmann-Schwingwer方程存在收敛的解，因此多体散射形式理论，有可能重新建立。由于核力和多体问题是当今核物理研究的两大难点，世界各国的科学家都在努力以图攻克它们，而且多体问题还是物理学的其它许多领域的难题，因而多体散射还是引起诸多研究学科广泛兴趣的课题。通过发展一些新的数学理论和方法，我们已得到一些有意义的结果。4.将量子分子动力学这种中高能量区域所用的理论分析方法扩展至较低能区，通过对相空间中初始位置和动量抽样增加限制条件。如结合能和实验值要求一致，平均核势，核内Pauli阻塞更强一些，在演化中能量和动量守恒等等。得到一个很稳定的初始基态。均方半径保持不弥散的时间可达1600fm/c，用于研究10.6MeV/u Ne~(20)+Al~(27)的实验分析过程中。另外，量子统计模型（QSM）主要描述中心核-核碰撞，将它和碎裂模型结合，作一些改进后，可以对核-核碰撞进行统一描述。5.在中能核反应研究中发现，核反应过程中有大量的中子，轻带电粒子以及中等质量碎片发射出来，可以将这些粒子发射机制大致分为两大类。其中一类可以归结为动力学发射过程的产物。另一类则可以归于统计发射的产物。在低能核反应中，其发射能谱的斜率的负倒数，可作为复合核的核温度。而在中能重离子核反应中，其发射能谱变得很复杂，不再具有Maxwell分布。通常的三源拟合所给出的温度参数，已不能反映物理实质。提出多阶矩分析方法用于分析中能核反应中统计发射规律及受动力学过程的影响。

N-arylamides from selenium-catalyzed reactions of nitroaromatics and amides in the presence of carbon monoxide and mixed organic bases

N-Arylamides were exclusively obtained in moderate to good yields from selenium-catalyzed reactions of nitroaromatics with amides in the presence of CO and mixed organic bases Et3N and DBU.

State-to-state dynamics of elementary chemical reactions using Rydberg H-atom translational spectroscopy

In this review, a few examples of state-to-state dynamics studies of both unimolecular and bimolecular reactions using the H-atom Rydberg tagging TOF technique were presented. From the H2O photodissociation at 157 nm, a direction dissociation example is provided, while photodissociation of H2O at 121.6 has provided an excellent dynamical case of complicated, yet direct dissociation process through conical intersections. The studies of the O(D-1) + H-2 --> OH+H reaction has also been reviewed here. A prototype example of state-to-state dynamics of pure insertion chemical reaction is provided. Effect of the reagent rotational excitation and the isotope effect on the dynamics of this reaction have also been investigated. The detailed mechanism for abstraction channel in this reaction has also been closely studied. The experimental investigations of the simplest chemical reaction, the H-3 system, have also been described here. Through extensive collaborations between theory and experiment, the mechanism for forward scattering product at high collision energies for the H+HD reaction was clarified, which is attributed to a slow down mechanism on the top of a quantized barrier transition state. Oscillations in the product quantum state resolved different cross sections have also been observed in the H+D-2 reaction, and were attributed to the interference of adiabatic transition state pathways from detailed theoretical analysis. The results reviewed here clearly show the significant advances we have made in the studies of the state-to-state molecular reaction dynamics.

In situ IR spectroscopic studies on molybdenum nitride catalysts: active sites and surface reactions

Recent IR spectroscopic studies on the surface properties of fresh Mo2N/gamma-Al2O3 catalyst are presented in this paper. The surface sites of fresh Mo2N/gamma-Al2O3, both Modelta+ (0<δ<2) and N sites, are probed by CO adsorption. Two characteristic IR bands were observed at 2045 and 2200 cm(-1), due to linearly adsorbed CO on Mo and N sites, respectively. The surface N sites are highly reactive and can react with adsorbed CO to form NCO species. Unlike adsorbed CO on reduced passivated one, the adsorbed CO on fresh Mo2N/gamma-Al2O3 behaves similarly to that of group VIII metals, suggesting that fresh nitride resembles noble metals. It is found that the surface of Mo nitrides slowly transformed into sulfide under hydrotreating conditions, which could be the main reason for the activity drop of molybdenum nitride catalysts in the presence of sulfur-containing species. Some surface reactions, such as selective hydrogenation of 1,3-butadiene, isomerization of 1-butene, and hydrodesulfurization of thiophene, were studied on both fresh and reduced passivated Mo2N/gammaAl(2)O(3) catalysts using IR spectroscopy. The mechanisms of these reactions are proposed. The adsorption and reaction behaviors of these molecules on fresh molybdenum nitride also resemble those on noble metals, manifesting the unique properties of fresh molybdenum nitride catalysts. Mo and N sites are found to play different roles in the adsorption and catalytic reactions on the fresh Mo2N/gammaAl(2)O(3) catalyst. Generally, Mo sites are the main active sites for the adsorption and reactions of adsorbates; N sites are not directly involved in catalytic reactions but they modify the electronic properties of Mo sites.

Photo-induced reactions in the ion-molecule complex Mg+-OCNC2H5

Ion - molecule complexes of magnesium cation with ethyl isocyanate were produced in a laser- ablation supersonic expansion nozzle source. Photo- induced reactions in the 1: 1 complexes have been studied in the spectral range of 230 - 410 nm. Photodissociation mass spectrometry revealed the persistent product Mg+ from nonreactive quenching throughout the entire wavelength range. As for the reactive channels, the photoproducts, Mg+OCN and C2H5+, were produced only in the blue absorption band of the complex with low yields. The action spectrum of Mg+(OCNC2H5) consists of two pronounced peaks on the red and blue sides of the Mg+ 3(2)P <-- 3(2)S atomic transition. The ground state geometry of Mg+ - OCNC2H5 was fully optimized at B3LYP/6- 31 - G** level by using GAUSSIAN 98 package. The calculated absorption spectrum of the complex using the optimized structure of its ground state agrees well with the observed action spectrum. Photofragment branching fractions of the products are almost independent of the photolysis photon energy for the 3P(x,y,z) excitations. The very low branching ratio of reactive products to nonreactive fragment suggests that evaporation is the main relaxation pathway in the photo- induced reactions of Mg+ (OCNC2H5). (C) 2003 American Institute of Physics.

Promoting effects in hydrogenation and hydrodesulfurization reactions on the zirconia and titania supported catalysts

Tetralin hydrogenation (HYD) and thiophene hydrodesulfurization (HDS) were studied for the supported MoS2 and WS2 sulfides, either non-promoted or promoted with Co and Ni. The supports used were ZrO2, alumina-stabilized TiO2 and pure alumina. Preparation of catalysts included presulfidation of non-promoted system with subsequent addition of promoter and resulfidation. It has been found that the nature of promoter plays determining role for the catalytic performance. The most active in both HYD and HDS reactions are Ni-promoted Mo and W catalysts, supported on ZrO2. (C) 2003 Published by Elsevier B.V.

Proton transfer reactions within the pyridazine-methanol cluster ion

The multiphoton ionization of the hydrogen-bonding cluster pyridazine-methanol (C4H4N2-CH3OH) was studied using a time-of-flight mass spectrometer at the wavelengths of 355 and 532 nm. At both wavelengths, a series of protonated C4H4N2-(CH3OH)(n)-H+ cluster ions were obtained. Relevant ab initio calculations were performed with HF and B3LYP methods. Equilibrium geometries of both neutral and ionic C4H4N2-CH3OH clusters, and dissociation channels and dissociation energies of ionic clusters, are presented. The results show that when C4H4N2-CH3OH is vertically ionized, C4H4N2H+ and CH3O are the dominant products via proton transfer reaction. A high energy barrier makes another channel corresponding to the production of C4H4N2H+ and CH2OH disfavored. (C) 2002 Elsevier Science B.V. All rights reserved.

Impact of carbon dioxide pressurization on liquid phase organic reactions: A case study on Heck and Diels-Alder reactions

Heck coupling reactions of methyl acrylate with various aryl bromides have been investigated using a Pd/TPP catalyst in toluene under pressurized CO2 conditions up to 13 MPa. Although CO2 is not a reactant, the pressurization of the reaction liquid phase with CO2 has positive and negative impacts on the rate of Heck coupling depending on the structures of the substrates examined. In the case of either 2-bromoacetophenone or 2-bromocinnamate, the conversion has a maximum at a CO2 pressure of about 3 MPa; for the former, it is much larger by a factor of 3 compared with that under ambient pressure. For 2-bromobenzene, in contrast, the conversion is minimized at a similar CO2 pressure, being half compared with that at ambient pressure

Impact of Carbon Dioxide Pressurization on Liquid Phase Organic Reactions: A Case Study on Heck and Diels–Alder Reactions

Heck coupling reactions of methyl acrylate with various aryl bromides have been investigated using a Pd/TPP catalyst in toluene under pressurized CO2 conditions up to 13 MPa. Although CO2 is not a reactant, the pressurization of the reaction liquid phase with CO2 has positive and negative impacts on the rate of Heck coupling depending on the structures of the substrates examined. In the case of either 2-bromoacetophenone or 2-bromocinnamate, the conversion has a maximum at a CO2 pressure of about 3 MPa;