1、姓學(xué)日20135 姓學(xué)日20135 第一次上CalculateHydrogenatomandHeliumatomuse3-21G/6-31G/6-311Gectronicenergy:kineticenergy,nuclearattractionenergy,electronHOMOandLUMO【計(jì)算結(jié)果】HOMOLUMO1 H 2 H 1 H 2 H 1 H 第一次上CalculateHydrogenatomandHeliumatomuse3-21G/6-31G/6-311Gectronicenergy:kineticenergy,nuclearattractionenergy,elect

2、ronHOMOandLUMO【計(jì)算結(jié)果】HOMOLUMO1 H 2 H 1 H 2 H 1 H 2 H -HOMOLUMO-1 He 1 He -1 He 第二次上Optimizationofthe#p opthf/6-Draw第二次上Optimizationofthe#p opthf/6-DrawthepotentialcurveofHeH+byDecidetheproducts:He/H+ orion of theScan R 0.4 30 0.2DrawthepotentialcurveofH2 byRHFandionof thecomponents(Hydrogen Scan H2 b

3、yRHF and UHFR 0.4 30 0.2#puhf/6-311Gguess=mixguess=alwaysR 0.4 30【計(jì)算結(jié)果】OptimizationoftheE(RHF)=-1.110032. Draw thepotentialcurveofHeH+ byE(RHF) =-2.85520 E(RHF) =-0.00000 E(RHF) =-2.85520 So the E(RHF) =E(RHF) =-2.85520 So the E(RHF) =-2.00011 E(RHF) =-0.49823E(RHF) =-2.49834tion productwill beHeand

4、 Finally thepotentialcurveof HeH+byRHF isshown DrawthepotentialcurveofH2 byRHF andH: E(RHF)=-0.498232908021 a.u. H:E(UHF)=-0.498232909202Finally thepotentialcurveof H2 by RHFand UHFWhytheRHFcalculationgivesawrongresultforThe RHF calculation does not go to the limit of two hydrogen atoms as R goes to

5、 For H2 the products of tion are two localized hydrogen t is, each is localized near one of the protons. However, in RHF calculation, both electrons are tooccupy the same spatial molecular orbital. Thismolecular orbitalis symmetryTherefore, independent of the bond length, both electrons are describe

6、d by exactly the same spatial wave function and have theTherefore, independent of the bond length, both electrons are described by exactly the same spatial wave function and have thesame probability distribution function in 3D space. All all, the RHF restricts electrons to occupy molecular orbital i

7、n pair, cannot properly tionunlessthe products of tionarebothclosed-第三次上Judgewhetheramethodissize-Methodsto udged: HFmp2cisd CalculationDocisd(qcisd)calculationforHe# vqzDo第三次上Judgewhetheramethodissize-Methodsto udged: HFmp2cisd CalculationDocisd(qcisd)calculationforHe# vqzDocisd(qcisd)calculationfo

8、rHe-He# vqzJudgewhetherE(He-CorrelationenergyfromdifferentlevelsofOptimizethehydrogenmoleculartogettheequilibriumbondlength. # opt hf/6-31g geom=connectivityDocisd and cidcalculationforthehydrogenmolecular atthe equilibriumbond#cisd/sto-3g(usebasissetsto-3g/6-ion of thevdzEquilibriumbondlengthbyHFan

9、dOptimizethefluorinemolecularby# opt vtzOptimizethefluorinemolecularby# opt vtzComparetheoptimized bondretMolecularelectronicstructureofDocalculation for #hf/6-31g geom=connectivity Get the electron configurationof CO,theleof N2 GiveHOMOandheformalism of【計(jì)算結(jié)果】JudgeGet the electron configurationof CO

10、,theleof N2 GiveHOMOandheformalism of【計(jì)算結(jié)果】Judgewhetheramethodissize-CorrelationenergyfromdifferentlevelsofBond length ofBasisContribution of0ion of theEquilibriumbondlengthbyHFandBond length (HF) =1.3291;Bond length(CISD) MolecularelectronicstructureofMolecularelectronicstructureofR=1.1307 Theelect

11、ronconfiguration of CO-0.14167 C1s + 0.25666 C2s -0.44474 C2pz + 0.65462 C3s -0.11134 C3pz +0.01239O1s -O2s + 0.27891 O2pz -0.05822O3S + 0.164080.46215 C2py +0.73836C3py -0.36142O2py -0.49624 第四次上FrequencyofCO.(keyword:HarmonicZPE.(keyword:zero-E第四次上FrequencyofCO.(keyword:HarmonicZPE.(keyword:zero-E

12、0 Computeit bytheequationE Computeitbythe equation【計(jì)算結(jié)果】OptimizationofHarmonicfrequencies=2427.9432cm-correction(ZPE) =0.005531E(SCF)=-112.775317E0=ZPE+E(SCF)=0.005531+(-112.775317)=-112.7697862Thermal correction toE(thermal)=0.007892E=E0+E(thermal)=0.007892+(-112.7697862)=-112.7618942第五次上Choiceof O

13、ptimizationoftheHFmolecular bymp4methodwithbasissets6-311G, 6-311G(3df,3pd) and 6-311+G(3df,3pd) separa#p opt mp4/basis 第五次上Choiceof OptimizationoftheHFmolecular bymp4methodwithbasissets6-311G, 6-311G(3df,3pd) and 6-311+G(3df,3pd) separa#p opt mp4/basis Get the optimized bondChoiceofndcompareittothe

14、 experimental data0.917 Optimization of the HF molecular by am1,pm3,hf and mp2 method with #p opt method/6-31+G(d)Get the optimized bondndcompareittothe experimental data0.917 AnionwithComputetheCO2molecularwithfunctionalb3lyp #p b3lyp/6-311+G(2d,2p)ComputetheCO2molecularwithHF#p hf/6-Gettheenergy givenby DFTand HFret【計(jì)算結(jié)果】Choiceof Bondlength d-type 和 p-type H 和 H 6-311G(3df,3pd)6-311G 基礎(chǔ)上引入了高角動量函數(shù)（F 原子df 軌道和H 原子軌道的極化函數(shù) ）， 計(jì)算結(jié)果精確度得到提高。 最后 6-311+G(3df,3pd基組在ChoiceofBondlength 軌道的極化函數(shù) ）， 計(jì)算結(jié)果精確度得到提高。 最后 6-311+G(3df,3pd基組在ChoiceofBondlength AM1:AM1 和Pm3 方法是半經(jīng)驗(yàn)計(jì)算