第三章Gaussian软件的使用new.ppt

Gaussian98/03的功能,分子的能量和结构过渡态的能量和结构振动频率红外和拉曼光谱（包括预共振拉曼）热化学性质成键和化学反应能量化学反应路径分子轨道原子电荷电多极矩,旋光性振动-转动耦合非谐性的振动分析和振动-转动耦合电子亲和能和电离势极化和超极化率（静态的和含频的）静电势和电子密度NMR屏蔽和磁化系数自旋-自旋耦合常数,几何构型的构建,GaussianView,例1：使用HF方法，优化H2O2分子,%chk=h2o2.chk%rwf=h2o2.rwf#phf/6-31goptH2O2energycalculation01HO10.9O21.41105.0H30.92105.01120.0,%chk=h2o2.chk%rwf=h2o2.rwf#phf/6-31goptH2O2energycalculation01H0.0000.0000.000O0.0000.9000.000O1.3501.2620.000H1.4641.742-0.752,内坐标表示笛卡尔直角坐标表示上述两个作业将对H2O2分子的结构进行完全优化，包括所有的键长键角和二面角。通过将内坐标定义成变量，可以对分子结构进行部分优化,%chk=h2o2.chk%rwf=h2o2.rwf#phf/6-31goptH2O2energycalculation01HO1B1O2B21A1H3B12A11D1B1=0.9B2=1.4A1=105.0D1=120.0通过对两个键长和键角使用同一变量定义可以控制分子的对称性,%chk=h2o2.chk%rwf=h2o2.rwf#phf/6-31goptH2O2energycalculation01HO1B1O2B21A1H3B12A11D1B1=0.9A1=105.0变量部分D1=120.0B2=1.4常量部分通过设定常量，可以使程序只对分子结构进行部分优化,例2：C2H4分子平面形分子,#HF/STO-3GOPTC2H4opt01CC1B1H1B22A1H1B22A13180.0H2B21A130.0H2B21A140.0B1=1.32B2=1.09A1=120.0,通过同一个变量控制C-H键长把二面角定义为180和0的常量来控制分子的平面构型,例3：CH3F分子分子点群C3V,#HF/STO-3GOPTCH3FC3vopt01CF1B1H1B22A1H1B22A13D1H1B22A13D1B1=1.38B2=1.09A1=110.6D1=120.0通过常量D1来控制C3V对称性,例4：NH3分子分子点群C3V,#HF/STO-3GOPTNH3C3vopt01NH1B1H1B12A1H1B12A13D1B1=0.99A1=109.0D1=120.0,例5：呋喃分子分子点群C2v,1.43,1.34,1.54,例6：乙炔分子直线形分子,练习,写出分子H2C=C=O分子输入坐标其中C=C:1.35C=O:1.20C-H:1.09写出苯分子内坐标C=C:1.30C-H:1.09,Gaussian的文件,Gjf计算任务文件Chk临时文件Rwf读写文件Out输出文件,Gaussian程序界面和输入文件的构造,%chk=water.chk%Section：行首以%开始，段后无空行%rwf=water.rwf#phf/6-31gscfcyc=250scfcon=8RouteSection：行首以#开始，段后加空行Waterennergytitle：作业的简要描述，段后加空行01MolecularSpecification：O分子说明部分，段后通常加空行H1R1H1R12a1R1=1.04a1=104.0,Gaussian作业的格式,%Section(link0),定义计算过程中的临时文件%chk=name.chk.chk文件在计算中记录分子几何构型，分子轨道，力常数矩阵等信息%rwf=name.rwf.rwf文件主要在作业重起时使用，当计算量比较大时，.rwf文件通常会非常大，此时需要将之分割保存内存使用控制%mem=n控制运行过程中使用内存的大小,可以以W或者MB，GB为单位default：6000000W48MB综合考虑到计算的需要和硬件水平，内存并非给得越多越好，最有效率的方法是根据作业类型估算所需要内存的大小,RouteSection,RouteSection以#开始，#控制作业的输出#N正常输出；默认(没有计算时间的信息)#P输出更多信息。包括每一执行模块在开始和结束时与计算机系统有关的各种信息(包括执行时间数据，以及SCF计算的收敛信息)#T精简输出：只打印重要的信息和结果。RouteSection主要由方法，基组，任务类型三部分组成Gaussian程序能完成的任务类型：,Gaussian程序中的部分关键词,Guess（初始轨道猜测）,GuessGuess=read要求从chk文件读取初始轨道猜测Guess=mixGuess=alter,SCF收敛,SCFCYC=ndefault=64收敛圈数,opt,优化平衡态opt=z-matrix内坐标，直角坐标直接是opt优化过渡态opt=(ts,z-matrix,noeigentest,readfc)optcyc=n,freq,Freq频率分析计算,常用的量子化学计算方法,量子力学理论,Born-Oppenheimer近似,非相对论近似,单电子近似,Hartree-Fock方程,Roothaan方程,自洽场从头算SCF-abinitio,密度泛函法DFT,超HF,LCMTO-X,AM1,C-EHMO,EHMO,IT-EHMO,MCNDO,CNDO,MINDO,INDO,MNDO,NDDO,PM3,MSW-X,DV-X,LCAO-X,从头算法AbInitio,半从头算法SlaterX,半经验法Semi-emperical,第一原理计算,常用的量子化学计算方法,量子力学理论,Born-Oppenheimer近似,非相对论近似,单电子近似,Hartree-Fock方程,Roothaan方程,自洽场从头算SCF-abinitio,密度泛函法DFT,超HF,LCMTO-X,AM1,C-EHMO,EHMO,IT-EHMO,MCNDO,CNDO,MINDO,INDO,MNDO,NDDO,PM3,MSW-X,DV-X,LCAO-X,从头算法AbInitio,半从头算法SlaterX,半经验法Semi-emperical,基组的选择,RouteSection采用自由格式，大小写不敏感同一行不同项之间可以使用空格，逗号和“/”连接；例：#phf/6-31gscfcyc=230scfcon=8#p,hf/6-31g,scfcyc=230,scfcon=8关键词可以通过keyword=option,keyword(option),keyword=(option1,option2,.)，keyword(option1,option2,.)指定例：#pHF/STO-3Gopt#pHF/STO-3Gopt=(TS,readfc),Title部分必须输入，但是程序并不执行，起标识和说明作用,TitleSection,Charge2/17=6,18=5,40=1/2;3/5=1,6=6,11=9,16=1,25=1,30=1/1,2,3;4/1;5/5=2,32=1,38=5/2;6/7=2,8=2,9=2,10=2,28=1/1;99/5=1,9=1/99;LeaveLink1atFriApr0801:21:372005,MaxMem=0cpu:1.0,重新打印作业输入和标准途径,作业执行过程,1/38=1/1;2/17=6,18=5,40=1/2;3/5=1,6=6,11=9,16=1,25=1,30=1/1,2,3;4/1;5/5=2,32=1,38=5/2;6/7=2,8=2,9=2,10=2,28=1/1;99/5=1,9=1/99;,L101L202L301L302L303L401L502L601L9999,L101读取标题和分子输入部分；L202坐标重新定向，计算对称性，检查变量；L301产生基组信息；L302计算重叠积分，动能积分和势能积分；L303计算多极积分；L401形成分子轨道初猜；L502自洽场迭代求解；L601布居数和相关分析；L9999完成计算和输出,L101读取标题和分子输入部分(EnterC:G03Wl101.exe)-h2osp-SymbolicZ-matrix:Charge=0Multiplicity=1O0.0.0.H0.6620.0.468H-0.6620.0.468LeaveLink101atFriApr0801:21:382005,MaxMem=6291456cpu:0.0,L202坐标重新定向，计算对称性，检查变量(EnterC:G03Wl202.exe)Inputorientation:-CenterAtomicAtomicCoordinates(Angstroms)NumberNumberTypeXYZ-1800.0000000.0000000.0000002100.6620000.0000000.468000310-0.6620000.0000000.468000-Distancematrix(angstroms):1231O0.0000002H0.8107210.0000003H0.8107211.3240000.000000StoichiometryH2OFrameworkgroupC2VC2(O),SGV(H2)Deg.offreedom2FullpointgroupC2VNOp4LargestAbeliansubgroupC2VNOp4LargestconciseAbeliansubgroupC2NOp2Standardorientation:-CenterAtomicAtomicCoordinates(Angstroms)NumberNumberTypeXYZ-1800.0000000.0000000.0936002100.0000000.662000-0.3744003100.000000-0.662000-0.374400-Rotationalconstants(GHZ):1289.0084222572.1186153396.2468433LeaveLink202atFriApr0801:21:402005,MaxMem=6291456cpu:1.0,L301产生基组信息(EnterC:G03Wl301.exe)Standardbasis:6-31G(6D,7F)Thereare7symmetryadaptedbasisfunctionsofA1symmetry.Thereare0symmetryadaptedbasisfunctionsofA2symmetry.Thereare2symmetryadaptedbasisfunctionsofB1symmetry.Thereare4symmetryadaptedbasisfunctionsofB2symmetry.Integralbufferswillbe262144wordslong.Raffenetti1integralformat.Two-electronintegralsymmetryisturnedon.13basisfunctions,30primitivegaussians,13cartesianbasisfunctions5alphaelectrons5betaelectronsnuclearrepulsionenergy10.8432720049Hartrees.IExCor=0DFT=FEx=HFCorr=NoneExCW=0ScaHFX=1.000000ScaDFX=1.0000001.0000001.0000001.000000IRadAn=0IRanWt=-1IRanGd=0ICorTp=0NAtoms=3NActive=3NUniq=2SFac=2.76D+00NAtFMM=60Big=FLeaveLink301atFriApr0801:57:332005,MaxMem=6291456cpu:1.0,L302计算重叠积分，动能积分和势能积分L303计算多极积分(EnterC:G03Wl302.exe)NPDir=0NMtPBC=1NCelOv=1NCel=1NClECP=1NCelD=1NCelK=1NCelE2=1NClLst=1CellRange=0.0.One-electronintegralscomputedusingPRISM.One-electronintegralsymmetryusedinSTVIntNBasis=13RedAO=TNBF=7024NBsUse=131.00D-06NBFU=7024LeaveLink302atFriApr0801:57:352005,MaxMem=6291456cpu:1.0(EnterC:G03Wl303.exe)DipDrv:MaxL=1.LeaveLink303atFriApr0801:57:362005,MaxMem=6291456cpu:0.0,L401形成分子轨道初猜(EnterC:G03Wl401.exe)HarrisfunctionalwithIExCor=205diagonalizedforinitialguess.ExpMin=1.61D-01ExpMax=5.48D+03ExpMxC=8.25D+02IAcc=1IRadAn=1AccDes=1.00D-06HarFok:IExCor=205AccDes=1.00D-06IRadAn=1IDoV=1ScaDFX=1.0000001.0000001.0000001.000000HarrisEn=-76.0428456360852Initialguessorbitalsymmetries:Occupied(A1)(A1)(B2)(A1)(B1)Virtual(A1)(B2)(B1)(A1)(B2)(B2)(A1)(A1)Theelectronicstateoftheinitialguessis1-A1.LeaveLink401atFriApr0801:57:372005,MaxMem=6291456cpu:0.0,L502自洽场迭代求解(EnterC:G03Wl502.exe)Warning!Cutoffsforsingle-pointcalculationsused.ClosedshellSCF:RequestedconvergenceonRMSdensitymatrix=1.00D-04within128cycles.RequestedconvergenceonMAXdensitymatrix=1.00D-02.Requestedconvergenceonenergy=5.00D-05.Nospecialactionsifenergyrises.UsingDIISextrapolation,IDIIS=1040.Integralsymmetryusagewillbedecideddynamically.KeepR1integralsinmemoryincanonicalform,NReq=424251.IEnd=18776IEndB=18776NGot=6291456MDV=6285583LenX=6285583SymmetrynotusedinFoFDir.MinBra=0MaxBra=1Meth=1.IRaf=0NMat=1IRICut=1DoRegI=TDoRafI=FISym2E=0JSym2E=0.,Cycle5Pass1IDiag1:E=-75.9273519590932Delta-E=-0.000003762089Rises=FDamp=FDIIS:error=5.91D-05atcycle5NSaved=5.NSaved=5IEnMin=5EnMin=-75.9273519590932IErMin=5ErrMin=5.91D-05ErrMax=5.91D-05EMaxC=1.00D-01BMatC=4.02D-08BMatP=1.89D-06IDIUse=1WtCom=1.00D+00WtEn=0.00D+00Coeff-Com:0.711D-02-0.177D-010.103D+00-0.460D+000.137D+01Coeff:0.711D-02-0.177D-010.103D+00-0.460D+000.137D+01Gap=0.746Goal=NoneShift=0.000RMSDP=4.58D-05MaxDP=1.68D-04DE=-3.76D-06OVMax=2.54D-04SCFDone:E(RHF)=-75.9273519591A.U.after5cyclesConvg=0.4576D-04-V/T=1.9895S*2=0.0000KE=7.673560164965D+01PE=-2.025358608090D+02EE=3.902963519532D+01LeaveLink502atFriApr0801:57:412005,MaxMem=6291456cpu:2.0,L601布居数和相关分析(EnterC:G03Wl601.exe)CopyingSCFdensitiestogeneralizeddensityrwf,ISCF=0IROHF=0.*PopulationanalysisusingtheSCFdensity.*Orbitalsymmetries:Occupied(A1)(A1)(B2)(A1)(B1)Virtual(A1)(B2)(B2)(B1)(A1)(A1)(B2)(A1)Theelectronicstateis1-A1.Alphaocc.eigenvalues-20.52887-1.44410-0.81350-0.57281-0.51130Alphavirt.eigenvalues-0.234900.331091.135361.163731.17135Alphavirt.eigenvalues-1.436361.500541.68694Condensedtoatoms(allelectrons):1231O8.0907140.3123390.3123392H0.3123390.374540-0.0445753H0.312339-0.0445750.374540Mullikenatomiccharges:11O-0.7153922H0.3576963H0.357696SumofMullikencharges=0.00000Atomicchargeswithhydrogenssummedintoheavyatoms:11O0.0000002H0.0000003H0.000000SumofMullikencharges=0.00000,Electronicspatialextent(au):=17.2272Charge=0.0000electronsDipolemoment(field-independentbasis,Debye):X=0.0000Y=0.0000Z=-2.4602Tot=2.4602Quadrupolemoment(field-independentbasis,Debye-Ang):XX=-6.8696YY=-4.2696ZZ=-6.1388XY=0.0000XZ=0.0000YZ=0.0000TracelessQuadrupolemoment(field-independentbasis,Debye-Ang):XX=-1.1103YY=1.4898ZZ=-0.3795XY=0.0000XZ=0.0000YZ=0.0000Octapolemoment(field-independentbasis,Debye-Ang*2):XXX=0.0000YYY=0.0000ZZZ=-1.6189XYY=0.0000XXY=0.0000XXZ=-0.5144XZZ=0.0000YZZ=0.0000YYZ=-0.9389XYZ=0.0000Hexadecapolemoment(field-independentbasis,Debye-Ang*3):XXXX=-4.8330YYYY=-4.5460ZZZZ=-5.2984XXXY=0.0000XXXZ=0.0000YYYX=0.0000YYYZ=0.0000ZZZX=0.0000ZZZY=0.0000XXYY=-1.6915XXZZ=-1.7089YYZZ=-1.5145XXYZ=0.0000YYXZ=0.0000ZZXY=0.0000N-N=1.084327200490D+01E-N=-2.025355816034D+02KE=7.673560164965D+01SymmetryA1KE=6.825101673560D+01SymmetryA2KE=0.000000000000D+00Symme