Heller-the semiclassical way to molecular spectroscopy

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1、368Acc.Chem.Res.1981,14,368-375physicallyreasonablesimplificationisneeded.intheIRCHamiltonian.AcalculationofthetunnelingOnewayofmakingtheratecalculationpracticablerateofthereactionHNC-HCNwascarriedoutabyistoreducetheproblemtoonedimension.ThefirstthesueoftheIRCHamiltonianofMillerandco-suchattempt

2、wasmadeintheabsoluteratecalculationworkers,46bobtainingtheinterestingresultthattherateofprotonmigrationintheenol-formmal~naldehyde.~~constantvalue-lo5s-lwasachievedabout8kcal/molWecanimagineapictureofalarge-amplitudenuclearbelowtheclassicalthreshold.motioninwhichthereactingsystemproceedsalongthe

3、ConcludingRemarksIRCwithnormalvibrationalmotionsintheplaneperpendiculartothedirectionofIRC.WeassumeinTheIRCapproachinchemodynamicalstudieshasthisapproximationa“vibrationaladiabati~ity”~~withjustbeguntotakeshape.Thepresentstageoftheregardtothelargeamplitude“translational”motiontheoryismainlytoest

4、ablishaframework.WiththisalongtheIRC.inmindthetheoryhasbeenformulatedtobeasbroadlyTheresult42formalonaldehydeprotonmigrationdidapplicableaspossible.Atthisstage,itmaybetolerablenotagreewithexperiment,althoughtheadiabaticap-tosacrificepragmatismbecauseoftheshortageofef-proachillustratedtheone-dime

5、nsionalreduction.Theficientcomputingprocedures.Itisexpectedthatintherateconstantobtained(-1014s-l)was102-103timesnearfuture,however,actualcalculationswillbecomelargerthanthatestimatedfromexperimentalstudiesfeasibleusinganewgenerationofcomputers.Inan-(-lollObviously,thisresultwaspartiallycausedti

6、cipationoftheseadvances,thetheoryshouldbearmedbythesmallpotentialbarrier,lessthan1kcal/mol,withmathematicalfoundations.adoptedinthecalculation.ThenumericalresultcouldInparticular,theglobalcharacterofconfigurationhavebeennodoubtimprovedbytakingthebarrierspaceshouldbeclarifiedbytheuseofglobalcoord

7、i-heighttobe11kcal/molwhichwasrecentlyobtainednates.Thesolutionofthemultidimensionalbytheoreticalcalculation^.^^SuchapresumptionisSchrodingerequations,therateproblemingeneralactuallyascertainedbyasimplertunnelingcalcula-nona