《分子电子结构》研究生课程教学资源（Electronic Structure of Molecules）ESM-3-BondOrder-Opt

Wiberg bond order&optimization2022calculation related topicsSPenergyNBO(localized)vsMO(delocalized)NBO Wiberg bond index:Optimization

Wiberg bond order & optimization 2022 calculation related topics • SP energy • NBO (localized) vs MO (delocalized) • NBO Wiberg bond index • Optimization

NBOWibergbondindexManually modified input%chk=...leg1-singlePoint\E201-nbo-bondOrder.chk#p hf/6-31g(d) pop=nboreadblank lineNBO chargeisFormaldehydeWibergbondindexcomputed bydefaultblank line01c0.000000000.000000000-0.5425000000.000000000.000000000.67750000H0.000000000.94000000-1.08250000H0.00000000-0.94000000-1.08250000blank lineSnbo bndidx SendPopulationhttp://gaussian.com/population/blanklineNBOnbo6.chem.wisc.eduNBO3embeddedinGaussian2

NBO Wiberg bond index 2 Manually modified input %chk= .\eg1-singlePoint\E2_01-nbo-bondOrder.chk #p hf/6-31g(d) pop=nboread blank line Formaldehyde Wiberg bond index blank line 0 1 C 0.00000000 0.00000000 -0.54250000 O 0.00000000 0.00000000 0.67750000 H 0.00000000 0.94000000 -1.08250000 H 0.00000000 -0.94000000 -1.08250000 blank line $nbo bndidx $end blank line Population http://gaussian.com/population/ NBO nbo6.chem.wisc.edu NBO3 embedded in Gaussian NBO charge is computed by default

NBOWiberg bond indexE2 01-nbo-bondOrder.outPopulationhttp://gaussian.com/population/WibergbondindexmatrixintheNAObasis:NBOnbo6.chem.wisc.edu2341AtomNBO3embeddedinGaussian1.C0.00001.86590.93750.9375GV6 open log file2.01.8659 0.0000 0.0420 0.0420results/bond3.H0.93750.04200.00000.0051properties/orderand show4.H0.93750.04200.00510.0000numberH,0.941.87OTotalLewis15.90738(99.4211%)0.94Valencenon-Lewis0.07123（0.4452%)Rydbergnon-Lewis0.02139(0.1337%)Totalunit 1 16.00000 (100.0000%)3

NBO Wiberg bond index 3 E2_01-nbo-bondOrder.out Wiberg bond index matrix in the NAO basis: Atom 1 2 3 4 - - - - - 1. C 0.0000 1.8659 0.9375 0.9375 2. O 1.8659 0.0000 0.0420 0.0420 3. H 0.9375 0.0420 0.0000 0.0051 4. H 0.9375 0.0420 0.0051 0.0000 Population http://gaussian.com/population/ NBO nbo6.chem.wisc.edu NBO3 embedded in Gaussian 1.87 0.94 0.94 - Total Lewis 15.90738 ( 99.4211%) Valence non-Lewis 0.07123 ( 0.4452%) Rydberg non-Lewis 0.02139 ( 0.1337%) - Total unit 1 16.00000 (100.0000%) GV6 open log file, results/bond properties/order and show number

Exercises2.Build the molecules below, calculate their bondorder, compare their MOs and NBOs, using themodel chemistry of hf/3-21gformicacidocta-1.3.5.7-tetraene

2.Build the molecules below, calculate their bond order, compare their MOs and NBOs, using the model chemistry of hf/3-21g. Exercises octa-1,3,5,7-tetraene formic acid

Potentialenergycurves(1-DpotentialenergysurfacesPotentialEnergy74pmRepulsiveAttractiveforcesforces-436kJ/mol-104kcal/molMoststablestate5

Potential energy curves (1-D potential energy surfaces) 5

Multidimensionalpotentialenergysurfaces(PEs)PESforwatermoleculeusaddlepointglobalmaximumlocalmaximumlocalminimumglobalminimumlocal minimumq,=H-O-HBondAngle104.5°0.0958nmTeporwsigClacier2oMoeryiaCanval RideRrdbankheThuatrosMadp6

Multidimensional potential energy surfaces (PES) 6 PES for water molecule

ModelpotentialenergysurfaceSecondOrderSaddlePointTransitionStructureATransitionStructureBMinimumforProductAMinimumforProductB0-0.5Second Order。0.5SaddlePoint0Valley-Ridge0.5-0.5InflectionPointMinimumforReactant-1Abstract axis, Hypersurface (3N-6 dimensions); multiplestates (So,S...); multiple pathways linking minima1J.Comp.Chem.2003,24,1514

Model potential energy surface 7 Abstract axis, Hypersurface (3N-6 dimensions); multiple states (S0 ,S1.); multiple pathways linking minima J. Comp. Chem. 2003, 24, 1514

Optimizationoptb3lyp/6-31g(d)旺Ethanoloptimization01c1.25018739-0.22107796-0.00000000H1.30967671-0.835971740.87365134H2.060289190.477946420.00000000H1.30967671-0.83597173-0.87365135c-0.086993800.542824180.00000000H-0.146483111.15771796-0.87365134H-0.146483111.157717950.873651350-1.16965321-0.39138596-0.00000000H-1.41192664-0.600439980.90509667

# opt b3lyp/6-31g(d) Ethanol optimization 0 1 C 1.25018739 -0.22107796 -0.00000000 H 1.30967671 -0.83597174 0.87365134 H 2.06028919 0.47794642 0.00000000 H 1.30967671 -0.83597173 -0.87365135 C -0.08699380 0.54282418 0.00000000 H -0.14648311 1.15771796 -0.87365134 H -0.14648311 1.15771795 0.87365135 O -1.16965321 -0.39138596 -0.00000000 H -1.41192664 -0.60043998 0.90509667 Optimization

Checkjob:Normaltermination,intermediatestructuresrsorfindproblemduringoptimization查找范围（I）：0916用七名称修改日期DETHANOL.LOG2019/9/916:01快速访问UREA.LOG2019/9/916:05桌面库此电脑网络打开（0)文件名(H)：文件类型（T）取消Gaussian OutputFiles(*,out*.log)Openas:AutoHelpTarget:SeparatenewmoleculegroupforeachfileOptions.VadIntemediateGeometries(GaussianOptimizationsOnly)

Check job: Normal termination, intermediate structures, or find problem during optimization 1 2

口XG1:M1:V1-ETHANOL.LOG(D:/DOC...0-1Hof9口XG1:M1:V1-Optimization Plot9 atoms, 26 electrons, neutral, singl. InquirePlotsculateResultsWindows HelpATotal EnergySummary...-155.0295Charge Distribution...-155.0300Surfaces/Contours...-155.0305-155.0310Vibrations...E-155.0315NMR....-155.0320UV-VIS....-155.0325155.0330Scan...-155.0335IRC/Path...2t155.03400Irajectory...-155.0345Optimization...TTUTTTTTTTTTTTTTTTTTTRTTT7.08.01.02.03. 04. 05.06.09.0oViewFileOptimization StepNumberStreamOutput FileO2