过渡金属表面反应能量学计算系统的开发(英文)

利用 VB6.0和 Access7.0开发了过渡金属表面反应能量学的计算系统 .该软件基于 U BI-QEP的理论方法 ,采用模块化设计 ,其功能模块有 3个 :(1)数据库模块 .利用该模块可以实现气相解离能以及小吸附基团在各种过渡金属表面吸附热的查询、添加与修改 ;(2 )化学吸附热计算模块 ,利用该模块可以调用数据库中的数据对吸附基团在不同吸附方式的吸附热进行计算 ;(3 )基元反应的活化能垒计算模块 .利用该模块可以对基元反应的活化内能进行计算 ,进而分析其反应的难易与历程 .该系统实现了 UBI-QEP的理论方法计算的程序化 。

清洁及氧修饰Cu(100)表面上CO_2加氢制甲醇反应的能量学

分别以清洁及氧修饰Cu（100）表面作为金属态铜和部分氧化态铜的表面模拟，用键级守恒-Morse势法研究了两种表面上CO2加氢制甲醇反应的能量学．计算结果表明：在两种表面上，CO2加氢制甲醇反应的优势反应途径均为“CO2，s→HCOOs→H2COs→CH3Os→CH3OHs”；与清洁铜表面上的相应基元步骤相比，在CU（100）-p（2X2）O表面上甲醇合成反应各基元步骤具有更低的活化能；HCOOs是合碳产物CH3OH、CO共同的前驱中间体，甲醇选择性由HCOOs的氢解反应与其解离生成COs及OHs竞争反应的相对速率决定；在清洁铜表面上，HCOOs的氢解反应与其解离生成COs及OHs竞争反应具有相似的活化能，而在氧修饰铜表面上，前者的活化能显著低于后者．因此，从反应能量学角度看，甲醇合成反应在部分氧化态铜表面上比在金属态铜表面上更有利．

基于反应能量学的多相催化反应分子设计系统

利用VB6.0语言开发多相催化的催化剂设计应用软件(HCMDS1.0)。该软件基于UBI-QEP 的理论方法,采用模块化设计,其功能模块有三:一是数据库模块,利用该模块可以实现气相解离键键能以及小吸附基团在各种过渡金属表面吸附热的查询、添加与修改;二是化学吸附热计算模块,利用该模块可以调用数据库中的数据对不同吸附方式的吸附热进行计算;三是基元反应的活化能垒计算模块,利用该模块可以对基元反应进行反应能量学计算,进而分析其反应的难易与历程。利用该系统可实现多相催化反应的催化剂优选和机理探讨。程序编写采用了Ac-cess 动态数据库和面向对象的编程技术,界面友好,运行稳定可靠。

基于反应能量学的多相催化机理推导系统

通过对催化反应机理推导过程的描述和分析,建立相应的程序算法。在此基础上进行程序和与之配套的数据库设计,开发了基于反应能量学的催化机理推导系统(MDHCS 2.0),详细讨论了算法的相关细节,包括推理规则、数据结构和具体流程。最后用合成氨反应解离式途径对本系统作验证,得出了令人满意的结果。

Quantum Dynamics of Oxyhydrogen Complex-Forming Reactions for the HO2 and HO3 Systems

Complex-forming reactions widely exist in gas-phase chemical reactions. Various complexforming bimolecular reactions have been investigated and interesting phenomena have been discovered. The complex-forming reactions usually have small or no barrier in the entrance channel, which leads to obvious differences in kinetic and dynamic characteristics compared with direct reactions. Theoretically, quantum state-resolved reaction dynamics can provide the most detailed microscopic dynamic mechanisms and is now feasible for a direct reaction with only one potential barrier. However, it is of great challenge to construct accurate potential energy surfaces and perform accurate quantum dynamics calculations for a complex polyatomic reaction involving deep potential wells and multi-channels. This paper reviews the most recent progress in two prototypical oxyhydrogen complex-forming reaction systems, HO2 and HO3, which are significant in combustion, atmospheric, and interstellar chemistry. We will present a brief survey of both computational and experimental work and emphasize on some unsolved problems existing in these systems.

Time-dependent Wave Packet Quantum Scattering Study of Reaction S（3p）＋H2→HS＋H on a New ab initio Potential Energy Surface 3A’

A new potential energy surface is presented for the triplet state 3At of the chemical reaction S（3P）＋H2 from a set of accurate ab initio data. The single point energies are computed using highly correlated complete active space self-consistent-field and multi-reference configuration interaction wave functions with a basis set of aug-cc-pV5Z. We have fitted the full set of energy values using many-body expansion method with an Aguado-Paniagua function. Based on the new potential energy surface, we carry out the time-dependent wave packet scattering calculations over the collision energy range of 0.8-2.2 eV. Both the centrifugalsudden approximation and Coriolis Coupling cross sections are obtained. In addition, the total reaction probabilities are calculated for the reactant H2 initially in the vibrational states v=0-3 （j=0）. It is found that initial vibrational excitation enhances the title reaction.

Electrochemical mechanism of rusticyanin (Rus.) isolated from A.ferrooxidans measured by Rus.-ZnS-QDs/L-Cys/Au electrode

Electrochimcal behaviors of rusticyanin （Rus.） isolated from Acidithiobacillus ferrooxidans were investigated through Rus.-ZnS-QDs/L-Cys/Au electrode. The cyclic voltammetric results indicate that rusticyanin immobilized on the surface of Rus.-ZnS-QDs/L-Cys/Au electrode can undergo a direct quasi-reversible electrochemical reaction. The immobilized rusticyanin is not denatured and still retains its activity in the temperature range of 19-43 ℃. The reduction ability of the protein increases and its oxidation ability becomes weak with the increase of pH from 6.0 to 7.8. Fe^2＋ ions in the solution can promote the electron transfer kinetics of the immobilized rusticyanin and make its peak potentials （φp） markedly move negatively.

Study of Total Process Energy Integration

The energy utilization consistency method in process integration extracts the key component of process energy utilization, and simplifies the procedure of process analysis and integration. The method allows the conversion of the total process energy integration into a synthesis problem of a pseudo-heat exchanger network. The advantages of using the energy utilization consistency and the pseudo-temperature methods are presented by two examples of integration of large-scale complex processes. The improved genetic algorithm is proved to be an effective tool in the retrofitting procedures.

Energy and entropy equations in coupled nonequilibrium thermal mechanical diffusive chemical heterogeneous system

In this paper we give an appropriate energy equation considering the diffusion and the energy production contributions of species for a complex coupled system with chemical reaction. It is shown that the contribution of the mass diffusion on the internal energy is the same whether it is introduced by the mass flow through the outer boundary or by the inner chemical reaction. In addition, the diffusion is a purely irreversible process and does not produce reversible entropy or entropy flow. Based on this theory a new entropy production rate equation is derived for the coupled thermal diffusive chemical heterogeneous system. The evolution equations of the heat conduction and the mass diffusion derived from this theory are fully consistent with the Fourier and Fick＇s laws.

Study of Cold Fusion Reactions Using Collective Clusterization Approach

Within the framework of the dynamical cluster decay model （DCM）, the in evaporation cross-sections （σ1n） of cold fusion reactions （Pb and Bi targets） are calculated for ZCN = 104-113 superheavy nuclei. The calculations are carried out in the fixed range of excitation energy ECN = 15 ± 1 MeV, so that the comparative analysis of reaction dynamics can be worked out. First of all, the fission barriers （Bf ） and neutron separation energies （S1n） are estimated to account the decreasing cross-sections of cold fusion reactions. In addition to this, the importance of hot optimum orientations of β24-deformed nuclei over cold one is explored at fixed angular momentum and neck-length parameters. The hot optimum orientations support all the target-projectile （t,p） combinations, which are explored experimentally in the cold fusion reactions. Some new target-projectile combinations are also predicted for future exploration. Further, the In cross-sections are addressed for ZCN = 104-113 superheavy nuclei at comparable excitation energies which show the decent agrement with experimental data upto ZCN = 109 nuclei. Finally, to understand the dynamics of higher-Z superheavy nuclei, the cross-sections are also calculated at maximum available energies around the Coulomb barrier and the effect of non-sticking moment of inertia （INS） is also investigated at these energies.