轨道计算

Several transient compounds were synthesized by the homo- and heterogeneous reactions of reactive halogen compounds, In-situ ultraviolet photoelectron spectroscopy and photoionization mass spectroscopy as well as theoretical calculations were used to study their molecular structures, stability and molecular orbital properties, their electronic structures and geometric structures were obtained for the first time; Simultaneously, the electronic structure and thermal dissociation of acetyl peroxynitrate and trifluoroacetyl peroxynitrate which have great importance in the atmospheric chemistry were studied; The substituent effects of series of halopyridines and halothiophenes were studied by the ultraviolet photoelectron spectroscopy method for the first time. The atmospheric chemical reaction between peroxyacetyl radicals with IO radicals as well as the dissociation of the most stable isomer of CH3COIO3 were calculated by density functional theory, it was found that the CH3COOIO2 isomer may be act as a new reservoir of inorganic iodine in the stratosphere.

通过活性卤素的系列均相与非均相化学反应合成了几种瞬态物种，采用原位紫外光电子能谱和光电离质谱结合量子化学理论计算对化合物的分子结构、稳定性以及分子轨道特性进行了研究，首次获得了这些物种的电子结构和几何结构的信息；同时研究了大气中有重要作用的乙酰过氧硝酸酯和三氟乙酰过氧硝酸酯的电子结构性质及热解过程；采用紫外光电子能谱手段首次研究了系列卤代吡啶和噻吩的取代基效应；通过量子化学理论计算研究了乙酰基过氧自由基与IO自由基的大气化学反应及其最稳定异构体CH3COOIO2的解离，发现该物种可能是无机碘化合物在平流层中的储库物种。

This paper presents the formula of the initial values of theorbital parameters— celestial longitudeφ_0 of the sun, right ascension ofascending nodeΩ_0 and argument of perigeeω_0, used for calculating orbitalheat flux received by satellite.

文章给出了卫星热分析空间外热流计算中所需要的轨道参数太阳黄经、交点赤经和近地点幅角的初值φ0、_、_的计算公式。

FLUENT is selected for the numerical simulation of hydrodynamic in fluidized bed because of the advantage of compute method and stabilization, astringency of computation of this software.

由于目前在硬件方面的限制，利用颗粒轨道模型对流化床进行模拟有很大的难度，而EULERIAN方法则可以以较少的计算花费得到两相各自的流体动力参数，同时也保证了计算的准确性、合理性，取得满意的结果。

The mechanism of the reaction was studiedin detail,in which excited state avaliable to carryout the excited state intramolecular proton transferreaction was recognized.The INDO/S-CI semiempiricalMO method was used to calculate transition energiesand oscillator strength,and assign spectra theore-tically,the calculated spectra values were basicallyconsistent with the experimental values.Themolecular orbital properties for the adjacent HOMO-LUMO of various kinds of conformersand anion species,thetransition properties and symmetry for thetransition from ground state to lower excited stateswere analysed,especially,no much study on theanion species all of the world.

位能曲线的求法满足反应坐标是反应过程中能量最小途径的定义，较详细地研究了各类反应的质子转移历程，认定在哪个激发态有利于发生激发态分子内质子转移反应，用INDO/S-CI半经验MO方法进行跃迁能和振子强度计算及光谱的理论指认，计算的光谱值和实验值基本吻合，并分析了各种异构体和阴离子的HOMO-LUMO附近的轨道性质，各跃迁态的跃迁性质和对称性，尤其是对阴离子的研究国内外尚不多见。

In the calculation for the nonadiabatic F2~P_(3/2, P_(1/2)+ H_2 reaction, it is foundthat Coriolis coupling and electronic coupling potential have a relatively minor effecton the reactivity from the ground state at lower translational energy, but a nonnegligible one at higher translational energy.

在本论文中我们把绝热的含时波包和RPD(reactant-product decoupling)反应散射计算扩展到了能够包括F 原子外壳层电子的自旋和轨道角动量的非绝热计算，并在ASW(Alexander-Stark-Werner)势能面上研究了这些反应的非绝热效应。

In this thesis,the AM1,MNDO,MINDO/3(mainly AM1)and INDO/S-CI semiempirical MO methods were used toinvestigate the excited-state intramolecular protontransfer reactions of salicylic acid derivatives—salicylic acid,methyl salicylate,salicylaldehyde,o-hydroxyaceto-phenone,salicylamide and 3-hydroxy-picolinamide (6 conformers and 2-3 anion species);2-(2'-hydroxy-5' methylphenyl) benzotriazole(4 conformers),2-(2' hydroxyphenyl) benzimidazole (3 conformers and 3anion species),Bis-2,5-(2-benzoxazolyl)hydroquinone(3 conformers),2-(2'-hydroxyphenyl)benzothiazole(2conformers) and 7-azaindole dimer (2 conformers).Theinvestigations were described as follows.Geometry optimization,relative stability andhydrogen bonding energy First,for sylicylic acid derivative molecules,the AM1,MNDO and MINDO/3 methods were used toinvestigate ground-state geometry optimization,energies,relative stabilities and hydrogen-bondingenergies on the five kinds of the molecules(designing 6 conformers and 2-3 anion species).Comparing with experimental data,the optimizedgeometry,the order of stability,the hydrogen-bonding energies and the distances between O-O in O-H..O hydrogen bonds by AM1 method were in agreementwith the experimental data,however,the C-C bondlengths optimized by MNDO and MINDO/3 were longer,C-O and O-H bond lengths were shorter;for C-N bondlengths,the results opitimized by MNDO method werethe same as those by AM1 method,nevertheless the C-Nbond lengths given by MINDO/3 method were muchshorter.For some sylicylic acid derivatives(e.g.methyl salicylate,salicylamide),the order ofstabilities on the conformers given by MNDO andMINDO/3 methods were not in agreement with theexisting conformers deduced by experimental methods,and the hydrogen bonding energies calculated by MNDO.and MINDO/3 methods were smaller.Second,the studyon the other systems found that the optimizedgeometry of the proton-transfered product with INDOmethod could not be obtained,only could theoptimized geometry of reactant be obtained,and thecalculated hydrogen bonding energies were greater.Many results of calculation indicated that the studyon the excited-state intramolecular proton transferreaction system using AM1 method was suitable andreliable.

本论文用AM1、MNDO、MINDO/3（主要是AM1）和INDO/S-CI半经验分子轨道方法对水杨酸衍生物系列——水杨酸、水杨酸甲酯、水杨醛、O-羟基乙酰苯酮、水杨酰胺和3-羟基吡啶酰胺（6种异构体和2-3种阴离子）；2-（2'-羟基-5'-甲基苯基）苯并三〓唑（4种异构体）；2-（2'-羟基苯基）苯并咪唑（3种异构体和3种阴离子）；2，5-二间氮杂氧茚氢醌（3种异构体）；2-（2'-羟基苯基）间〓杂硫茚（2种异构体）和7-〓吲哚二体（2种异构体）的激发态分子内质子转移反应在以下几个方面进行了较系统的理论研究：几何构型优化和相对稳定性及氢键能首先以水杨酸衍生物系列分子为例，用AM1、MNDO和MINDO/3方法考察了5种分子（每种分子设计6种异构体和2-3种阴离子）的基态几何构型优化，能量、相对稳定性和氢键能计算，通过和实验数据进行比较，AM1方法给出的优化几何构型、稳定性次序、氢键能和O—H。。。O氢键的0—0距离与实验数据吻合最好，MNDO和MINDO/3方法优化的C-C键长偏长，C-O键和O-H键长偏短；对于C-N键长，MNDO和AM1优化结果差别不大，而MINDO/3给出了过短的C-N键长，MNDO和MINDO/3方法给出的有些水杨酸衍生物分子（如水杨酸甲酯和水杨酰胺）异构体的稳定性次序和实验上推测的可存在异构体结果不一致，MNDO和MINDO/3方法给出的氢键能偏低，对其他体系的研究发现INDO方法常常不能得到质子转移产物的优化几何构型，只能得到反应物的优化构型，并且估算的氢键能偏高，大量的计算结果表明AM1方法对本论文研究的激发态分子内质子转移反应体系是适宜和可靠的。

the title compound was synthesized and its structure was studied in theory.the schiff base compound was synthesized by condensation of paeonol with furylfurylamine,then it was deoxidized by sodium borohydried.the energies,bound lengths,bound angles,the net charges of main atom and contributive percents of frontier orbital in the title compound have been calculated by software hyperchem 7.0 in half experience method.the yield rate of title compound was 65.6%.the result of calculation showed that the most of the bond lengths and angles in the system were in the the normal range,negative charge mainly concentrate on o1,o2,o3 and n1.the title compound behaves as quadridentate ligand.

目的合成标题化合物并对其结构进行了理论研究。方法以丹皮酚和糠胺为原料合成席夫碱，经硼氢化钠还原得标题化合物；使用hyperchem7.0程序，用半经验方法计算了化合物分子中能量分布、主要键长、键角以及主要原子的净电荷分布和前言轨道分布。结果标题化合物，收率65.6%；计算结果分析表明，分子中主要原子之间的键长、键角基本在正常的范围内；负电荷主要集中于o1，o2，o3和n1上。

The inner reorganization energy and the exothermicity of the reaction are then determined. Closed shell HF SCF calculations have been carried out for the systems Tryptophy1-Tyrosine and Tyrosyl-Tryptophan for different values of R, and the Koopmans^,theorem is invoked to estimate the energy level splitting A.From the obtained A~m~i~n, the values of electron transfer matrix element V~D~A are determined to be 0.96kJ. mol^-^1 and 0.87kJ.mol^-^1 for Tryptophyl-Tyrosine and Tyrosyl- Tryptophan, respectively.

对色氨酰酪氨酸和酪氨酰色氨酸体系进行闭壳层HF自洽场计算，按Koopmans定理计算体系分子轨道分裂能值A，在R约为0处发现了A的极小值，从而获得色氨酰酪氨酸及酪氨酰色氨酸体系分子内电子转移的电子转移矩阵元V~D~A分别为0.96kJ.mol^-^1和0.87kJ.mol^-^1。

I can calculate the motions of the heavenly, but not the madness of people.

& &我可以计算天体运行的轨道，却无法计算人性的疯狂。

The tracking information is relayed to the master control station in the Consolidated Space Operations Centerlocated at Schriever Air Force base in Colorado Springs. The master control station uses this date to make precise near-future predictions of the satellite orbits, and their clock correction parameters.

追踪的信息都发往位于Clolrado Springs空军基地的'统一宇宙操作中心'，这个中心把收到的数据进行计算以更精确的计算出卫星将要行使的轨道和卫星时钟校正参数。

As she looked at Warrington's manly face, and dark, melancholy eyes, she had settled in her mind that he must have been the victim of an unhappy attachment.

每逢看到沃林顿那刚毅的脸，那乌黑、忧郁的眼睛，她便会相信，他一定作过不幸的爱情的受害者。

Maybe they'll disappear into a pothole.

也许他们将在壶穴里消失