3 激發(fā)態(tài)S₁優(yōu)化

熒光是冷光現(xiàn)象，一般指發(fā)生在自旋單重態(tài)之間的輻射過程。根據(jù)Kasha規(guī)則，它是最低激發(fā)態(tài)到基態(tài)的發(fā)射，一般為S₁態(tài)到S₀態(tài)。為了模擬熒光過程，還需要對激發(fā)態(tài)S₁做結(jié)構(gòu)優(yōu)化和頻率計算，得到log文件和fchk文件，為后續(xù)MOMAP的計算做準備。泛函和基組分別為M062x和Def2SVP，gjf文件如下：

%nprocshared=32

%mem=6GB

%chk=s1opt.chk

#P opt freq M062x/Def2SVP TD(nstates=3,root=1)

Title Card Required

0 1

C 1.565649 -4.134284 -0.176953

C 1.643599 -2.628388 -0.152751

C 2.886000 -2.003080 -0.112539

C 3.020859 -0.613479 -0.088550

N 4.325420 -0.044576 -0.036499

C 5.278240 -0.466495 -0.995386

C 4.884618 -0.626003 -2.332720

C 5.799622 -1.064339 -3.285338

C 7.121820 -1.335486 -2.928150

C 7.515238 -1.172730 -1.598991

C 6.603320 -0.752040 -0.633991

C 4.698175 0.744156 1.076980

C 4.091832 0.542012 2.325047

C 4.427797 1.352319 3.406784

C 5.379893 2.362883 3.271786

C 5.988191 2.561344 2.030562

C 5.647767 1.769732 0.937881

C 1.876752 0.211899 -0.120738

C 0.588755 -0.407573 -0.126231

C 0.473733 -1.832327 -0.148612

C -0.837555 -2.410247 -0.178205

C -1.959943 -1.640762 -0.161854

C -1.876694 -0.212016 -0.120592

C -0.588696 0.407452 -0.126517

C -0.473668 1.832190 -0.149905

C 0.837623 2.410088 -0.179888

C 1.960009 1.640614 -0.162984

C -1.643530 2.628249 -0.154622

C -2.885933 2.002973 -0.113981

C -3.020804 0.613392 -0.088992

N -4.325380 0.044559 -0.036541

C -4.698230 -0.743314 1.077511

C -4.091928 -0.540291 2.325457

C -4.428022 -1.349755 3.407783

C -5.380213 -2.360326 3.273499

C -5.988485 -2.559645 2.032401

C -5.647934 -1.768883 0.939143

C -5.278162 0.465750 -0.995788

C -4.884527 0.624147 -2.333249

C -5.799513 1.061738 -3.286228

C -7.121702 1.333222 -2.929264

C -7.515137 1.171550 -1.599978

C -6.603236 0.751616 -0.634632

C -1.565577 4.134127 -0.179894

H 2.565826 -4.573123 -0.163055

H 1.054624 -4.497512 -1.075888

H 1.015461 -4.526102 0.685940

H 3.789152 -2.604760 -0.095814

H 3.860188 -0.404796 -2.611283

H 5.478783 -1.182339 -4.316028

H 7.834889 -1.669709 -3.674725

H 8.537506 -1.389762 -1.303667

H 6.910123 -0.642734 0.399820

H 3.355698 -0.245579 2.436971

H 3.946094 1.182749 4.365139

H 5.642450 2.988231 4.118776

H 6.724707 3.349483 1.905053

H 6.110094 1.939850 -0.027830

H -0.934317 -3.489037 -0.217496

H -2.937842 -2.104213 -0.185630

H 0.934386 3.488850 -0.219935

H 2.937915 2.104041 -0.187063

H -3.789080 2.604673 -0.097685

H -3.355727 0.247315 2.436831

H -3.946346 -1.179515 4.366033

H -5.642871 -2.985014 4.120945

H -6.725084 -3.347795 1.907449

H -6.110250 -1.939666 -0.026456

H -3.860104 0.402673 -2.611627

H -5.478667 1.178888 -4.317013

H -7.834757 1.666861 -3.676114

H -8.537402 1.388848 -1.304838

H -6.910046 0.643140 0.399265

H -1.015334 4.526556 0.682686

H -2.565752 4.572979 -0.166245

H -1.054607 4.496714 -1.079120

作業(yè)完成后在log文件中找到最后一個Excited State 1為S₁激發(fā)能，Total Energy為電子態(tài)能量。

4 激發(fā)態(tài)T₂、T₃優(yōu)化

由于本案例后續(xù)會用MOMAP做T₂→S₁態(tài)和T₃→S₁態(tài)的反系間竄越速率計算，所以前期還需要量化軟件做激發(fā)態(tài)T₂和T₃的結(jié)構(gòu)優(yōu)化和頻率計算，得到log文件和fchk文件。泛函和基組分別為M062x和Def2SVP，T2.gjf文件如下：

%nprocshared=32

%mem=6GB

%chk=t2.chk

#P opt freq M062x/Def2SVP TD(triplets，nstates=6,root=2)

Title Card Required

0 1

C 1.565649 -4.134284 -0.176953

C 1.643599 -2.628388 -0.152751

C 2.886000 -2.003080 -0.112539

C 3.020859 -0.613479 -0.088550

N 4.325420 -0.044576 -0.036499

C 5.278240 -0.466495 -0.995386

C 4.884618 -0.626003 -2.332720

C 5.799622 -1.064339 -3.285338

C 7.121820 -1.335486 -2.928150

C 7.515238 -1.172730 -1.598991

C 6.603320 -0.752040 -0.633991

C 4.698175 0.744156 1.076980

C 4.091832 0.542012 2.325047

C 4.427797 1.352319 3.406784

C 5.379893 2.362883 3.271786

C 5.988191 2.561344 2.030562

C 5.647767 1.769732 0.937881

C 1.876752 0.211899 -0.120738

C 0.588755 -0.407573 -0.126231

C 0.473733 -1.832327 -0.148612

C -0.837555 -2.410247 -0.178205

C -1.959943 -1.640762 -0.161854

C -1.876694 -0.212016 -0.120592

C -0.588696 0.407452 -0.126517

C -0.473668 1.832190 -0.149905

C 0.837623 2.410088 -0.179888

C 1.960009 1.640614 -0.162984

C -1.643530 2.628249 -0.154622

C -2.885933 2.002973 -0.113981

C -3.020804 0.613392 -0.088992

N -4.325380 0.044559 -0.036541

C -4.698230 -0.743314 1.077511

C -4.091928 -0.540291 2.325457

C -4.428022 -1.349755 3.407783

C -5.380213 -2.360326 3.273499

C -5.988485 -2.559645 2.032401

C -5.647934 -1.768883 0.939143

C -5.278162 0.465750 -0.995788

C -4.884527 0.624147 -2.333249

C -5.799513 1.061738 -3.286228

C -7.121702 1.333222 -2.929264

C -7.515137 1.171550 -1.599978

C -6.603236 0.751616 -0.634632

C -1.565577 4.134127 -0.179894

H 2.565826 -4.573123 -0.163055

H 1.054624 -4.497512 -1.075888

H 1.015461 -4.526102 0.685940

H 3.789152 -2.604760 -0.095814

H 3.860188 -0.404796 -2.611283

H 5.478783 -1.182339 -4.316028

H 7.834889 -1.669709 -3.674725

H 8.537506 -1.389762 -1.303667

H 6.910123 -0.642734 0.399820

H 3.355698 -0.245579 2.436971

H 3.946094 1.182749 4.365139

H 5.642450 2.988231 4.118776

H 6.724707 3.349483 1.905053

H 6.110094 1.939850 -0.027830

H -0.934317 -3.489037 -0.217496

H -2.937842 -2.104213 -0.185630

H 0.934386 3.488850 -0.219935

H 2.937915 2.104041 -0.187063

H -3.789080 2.604673 -0.097685

H -3.355727 0.247315 2.436831

H -3.946346 -1.179515 4.366033

H -5.642871 -2.985014 4.120945

H -6.725084 -3.347795 1.907449

H -6.110250 -1.939666 -0.026456

H -3.860104 0.402673 -2.611627

H -5.478667 1.178888 -4.317013

H -7.834757 1.666861 -3.676114

H -8.537402 1.388848 -1.304838

H -6.910046 0.643140 0.399265

H -1.015334 4.526556 0.682686

H -2.565752 4.572979 -0.166245

H -1.054607 4.496714 -1.079120

作業(yè)完成后在log文件中找到最后一個Excited State 2為T₂激發(fā)能，Total Energy為電子態(tài)能量。

同樣對T₃優(yōu)化可得T₃態(tài)能量。結(jié)果顯示T₃電子態(tài)能量小于T₂態(tài)能量，這表示T₂與T₃態(tài)在遠離Frank-Condon區(qū)優(yōu)化的過程中可能存在勢能面交叉，使得最終優(yōu)化的T₃極小點能量小于T₂。