分子光谱基础

iNtvreEEEEEEE+++++=EeErEvEtEN[NMR(nuclearmagneticresonance)ESR(EPR)-electronspinresonance(electronparamagnetic)]Ei10-18eV,rvemnnmhEEnnnnln++=-==1E=Ee+Ev+Er.10023CH4,CO2E0-210-6106109103106X-10.11041051202514001040.051IR10425140010-40.0510410-210-610710-410-8/m/cm-1E/eVn10-4-0.05eVm1m2rrmmmr2121+=21mrmr=,rrr=+21m1r1=m2(r-r1)rmmmr2112+==+=222211rmrmI222121rrmmmmm=+C,m1v1=r1,m2v2=r22222112121vmvmE+==222211)(21)(21wwrmrm+2221wmr221wIIM22===m,v,p=mv,22mvT=I,,M=I,22wIT=IMH2ˆˆ2=yyEIM=2ˆ22224)1(phJJM+=J=0,1,2,···IhJJEr228)1(p+=J—:1±=ΔJJJ+1chJEJEchE)()1(~-+=Δ=n=])1()1)(2[(82JJJJIch+-++p×2)1(82+JIchp)1(2+JBIchB28p=B2~=Δn==300K10-28kg,10-7cm0.996)exp(11kTEEnnJJJJ--=++3.5.1H35Cl=21.18,42.38,63.54,84.72,105.91cm-1,nnΔ=21.18cm-1=2B=Ich282p×I=Bch28p1812234sm9979.2m1059.108sJ106262.6---⋅××××⋅×p=2.64310-47kg·m2ClHClHmmmm+=m2310023.6)350079.1(350079.1××+×=1.6266810-27kgmIr==127.5pm===HClDClHClDCl=1~n)1(21+JB)1(412+JcIhp=2~n)1(22+JB)1(422+JcIhp=-=Δ21~~~nnn)11)(1(4212IIJch-+p)1(~211II-n)1(~211mmn-1~,~nnΔ21mm1221221221~~mmmmnn===rrII(1)re,r=r1+r2r-re=q2221)(21kqrrkVe=-=k——2111)(21dtdrmT=2222)(21dtdrmT=rmmmr2121+=rmmmr2112+=221)(21dtdrTTTm=+=q=r-re2221)(21qPdtdqTmm==22228ˆdqdhTmp-=yympEkqdqdh=+-]218[22222Hv)()21exp()!2()(2122141qHqvvvvaapay⋅-⋅=-vvqH)1()(21-=a⋅)exp(2qavvqdd)(21a)exp(2qa-hmnpa24=vnhvEv)21(+=v=012…nh21)21exp()(2410qapay-=nhE210=)21exp()4(24131qqapay-⋅⋅=nhE)211(1+=1±=Δnvy1+vyeechcEnnn~/~==Δ=en~mpnkce21~=2MorseVreerr-2)]}(exp[1{eerrDV---=b⋅⋅⋅+-+-+-+=333222)(!31)(!21)()()(eeeerrdrVdrrdrVdrrdrdVrVrVreVV(re)=0,0=drdV,4)(err-3'2)()(21)(eerrkrrkrV-+-=eevxhvvhvE2)21()21(+-+=nv=0,1,2,…x0≠Δm1.2.…,0=Δn,1±,2±,3±300K)exp(11kTEEnnvvvv--=++=0.0096v=0v=0v=vv=1,2,3,401020304x=-=hcEEv0~nxvv2)21()21[(+-+evx~)]421(--=evxvn~])1(1[+-]21[~~1xe-=nn]31[~2~2xe-=nn]41[~3~3xe-=nn]51[~4~4xe-=nnen~HCl]21[~xe-n=2885.9cm-1]31[~2xe-n=5668.0cm-1en~=2987.7cm-1x=0.0174en~mpnkce21~=mnp222~4eck==516.3Nm-1MorsexhDee4n=xhhDDeeenn41210+-=en~xD0=8.2410-10J.3—eeJvxhvvhvE2,)21()21(+-+=n+)1(+JBchJ——…2,1±±=Δv…1±=ΔJv=0v=1JJ/=n~+1~n])1()1([/JJJJB+-+JJJ-=Δ/+1-1:1+=ΔJ1~n1~nR1-=ΔJ1~n1~nP.0=ΔJ4B.4.n3n.=3n-3()-3()=3n-6=3n-3()-2()=3n-5————mpnke21=,∫tmjjdbaH2O=33-6=3CO2=33-5=41383cm-1H2O3152cm-12,5331cm-1,6872cm-12+2~n32~~nn+2~n3~nCHNCHNOCHOSP≡CHstretchCH2,CH3stretchC≡CstretchCH3bendRaman192119281930228RamanRamanRamanabRamanEaEbRamanRamanH-HRamanH-H4400cm-1=574.9N·m-1RamanbbaaEhEh+=+nnnnnΔ=-=-=ΔhhEEEbaab)(en~k1~20eV10-15s,v=0v=v—(Frank—Condon).λmax242.5nmε=13100