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1、带有溶剂效应的荧光发射光谱计算Step1:Groundstategeometryoptimizationandfrequencies(equilibriumsolvation平衡溶剂化：在电子结构不发生改变时，若分子几何结构发生变化则溶剂也跟着变化). Thisisastandard OptFreqcalculationonthegroundstateincludingPCMequilibriumsolvation.获得带有溶剂效应的基态稳定几何结构%chk=01-ac#B3LYP/6-31+G(d,p)OptFreqSCRF=(Solvent=Etha
2、nol)Acetaldehydegroundstate01分子说明自行补充Hereistheenergyofthegroundstateoptimizedgeometryinsolution:SCFDone:E(RB3LYP)=-153.851761719A.U.after1cyclesStep2:Verticalexcitationwithlinearresponsesolvation. ThisisaTD-DFTcalculationoftheverticalexcitation,thereforeatthegroundstateequilibriu
3、mgeometry,withthedefaultsolvation:linearresponse,non-equilibrium.Weperformasingle-pointTD-DFTcalculation,whichdefaultstonon-equilibriumsolvation.Theresultsofthisjobwillbeusedtoidentifywhichstateorstatesareofinterestandtheirordering.Theseresultsgiveareasonabledescriptionofthesolva
4、tionoftheexcitedstate,butnotquiteasgoodasthatfromastate-specificsolvationcalculation.Inthiscase,weseethatthen→π*state(产生第一激发态的跃迁方式)isthefirstexcitedstate.Next,wewillusethestate-specificmethodtoproduceabetterdescriptionoftheverticalexcitationstep.复制以上step1中的01-ac.chk,并将复制文件命名为02-a
5、c.chk，然后执行如下操作计算紫外跃迁吸收光谱。下边这个计算默认为non-equilibriumsolvation。垂直激发默认为NonEq过程，但此时没有使用EI，表示并未调整激发态结构的electrondensity使其自洽于环境(几何结构与step4的终态几何结构全同)。%chk=02-ac#B3LYP/6-31+G(d,p)TD=NStates=6SCRF=(Solvent=Ethanol)Geom=CheckGuess=ReadAcetaldehyde:linearresponseverticalexcitedstates01Theverti
6、calexcitation(absorption)tofirstexcitedstatefromthenon-equilibriumsolvationlinearresponsecalculation:发生电子跃迁时，溶剂来不及运动，所以叫做non-equilibriumsolvationlinearresponseExcitedState1:Singlet-A"4.3767eV283.28nmf=0.0000=0.000Thus,thegroundstatetofirstexcitedstateabsorptionisat283.28nm,
7、computedviathelinear-responseapproach.Step4:Relaxationoftheexcitedstategeometry. Next,weperformaTD-DFTgeometryoptimization,withequilibrium,linearresponsesolvation(在第一激发态的垂直结构基础上进行结构弛豫，此过程不发生电子跃迁，溶剂也跟着调整，所以为equilibrium过程),inordertofindtheminimumenergypointontheexcitedstatepotentia
8、lenergysurface.SincethisisaTD-DFToptimiz
