激发三重态T1的结构优化和频率计算的过程

上一期介绍了使用量化软件BDF进行Ir(ppy)₃的基态S0的结构优化和频率计算。这一期将介绍第一激发三重态T1的结构优化和频率计算的过程。

Irppy3_t1.xyz内容如下：

准备Ir(ppy)₃分子结构的xyz文件如下：

61

Ir         -0.00021963       0.00084588       0.01424181

C           2.59517396      -1.31710199      -0.58086411

C           2.23709967       0.40664133      -2.11684705

C           3.82729349      -1.60375453      -1.18851600

C           2.03843393      -2.01080680       0.57861773

C           3.44334868       0.17103124      -2.75937571

H           1.56522101       1.20579483      -2.43942631

C           4.25160770      -0.86138490      -2.27959559

H           4.44860577      -2.40719663      -0.79331056

C           2.69382363      -3.08153995       1.20802708

H           3.74085930       0.78654308      -3.60925966

H           5.21146469      -1.08097154      -2.75293386

C           0.24421139      -2.16970311       2.17811922

C           2.12763720      -3.69300459       2.31682204

H           3.65478554      -3.44259873       0.83261331

C           0.89831764      -3.22978876       2.79882363

H          -0.71249803      -1.82386403       2.57651491

H           2.63779958      -4.52517522       2.80699129

H           0.44660698      -3.70582388       3.67403286

C          -1.72035469       0.07933387       1.04722001

C          -2.76313413      -0.76101290       0.56881686

C          -2.01025266       0.87257612       2.17113445

C          -4.02037491      -0.79383502       1.19368759

C          -2.43582629      -1.59048558      -0.58889316

C          -3.25751526       0.83538180       2.78746398

H          -1.23410642       1.52839366       2.57249446

C          -4.27126073       0.00210869       2.30157161

H          -4.81180920      -1.44586060       0.81528272

C          -3.29617560      -2.51740929      -1.19724703

H          -3.44731484       1.46422538       3.66217358

H          -5.24881003      -0.02406750       2.78811438

C          -0.75837785      -2.14128396      -2.11906742

C          -2.86048279      -3.25738595      -2.28544733

H          -4.30328496      -2.65589425      -0.80436165

C          -1.56140370      -3.07140479      -2.76199645

H           0.27022263      -1.95736074      -2.43892538

H          -3.52729093      -3.98185076      -2.75888376

H          -1.17316801      -3.63790053      -3.60937499

N          -1.18202102      -1.42059810      -1.07683756

C          -0.15520348       2.90563657      -0.58971088

C          -1.46338895       1.72871866      -2.12679953

C          -0.52211987       4.11414752      -1.20165791

C           0.72001848       2.77388462       0.57312738

C          -1.86121725       2.88919512      -2.77366419

H          -1.81791319       0.74611096      -2.44764729

C          -1.37377275       4.10694585      -2.29536844

H          -0.13934280       5.05543436      -0.80755998

C           0.92315032       1.45037015       1.05224777

C           1.31701199       3.87857243       1.20194236

H          -2.54044030       2.83638038      -3.62545723

H          -1.66304625       5.04659184      -2.77183207

C           1.74847348       1.30397901       2.18095829

C           2.12513377       3.69714085       2.31457434

H           1.15050564       4.89023888       0.82308669

C           2.33662182       2.40226678       2.80117156

H           1.92559465       0.30363467       2.58285826

H           2.58863363       4.55643063       2.80428368

H           2.97087444       2.25159426       3.67958431

N          -0.63391888       1.73510439      -1.07938881

N           1.82331270      -0.31615001      -1.07209969

C           0.78888390      -1.52564414       1.05342887

选择Simulator → BDF → BDF，在界面中设置参数。在Basic Settings界面中的Calculation Type选择TDDFT-OPT+Freq，方法采用默认的PBE0泛函，基组在Basis中的All Electron类型中，选择Def2-SVP。Basic Settings界面中的其它参数使用推荐的默认值，不需要做修改。

SCF Settings界面中将Use MPEC+COSX Acceleraton的默认勾选去掉。SCF Settings界面中的其它参数使用推荐的默认值，不需要做修改。

TDDFT Settings面板中将Use MPEC+COSX Acceleraton的默认勾选去掉。Mutiplicity选择Triplet，Convergence Threshold选择Very Tight。TDDFT Settings界面中的其它参数使用推荐的默认值，不需要做修改。

OPT Settings和Freq Settings面板的参数使用推荐的默认值，不需要做修改。之后点击 Generate files 即可生成对应计算的输入文件。选中生成的bdf.inp文件，右击选择open containing folder进入所在文件夹，在bdf.inp的$tddft模块中加入：

Gridtol

1E-6

bdf.inp内容如下：

$compass

Title

C33H24IrN3

Geometry

Ir -0.00021963 0.00084588 0.01424181

C 2.59517396 -1.31710199 -0.58086411

C 2.23709967 0.40664133 -2.11684705

C 3.82729349 -1.60375453 -1.18851600

C 2.03843393 -2.01080680 0.57861773

C 3.44334868 0.17103124 -2.75937571

H 1.56522101 1.20579483 -2.43942631

C 4.25160770 -0.86138490 -2.27959559

H 4.44860577 -2.40719663 -0.79331056

C 2.69382363 -3.08153995 1.20802708

H 3.74085930 0.78654308 -3.60925966

H 5.21146469 -1.08097154 -2.75293386

C 0.24421139 -2.16970311 2.17811922

C 2.12763720 -3.69300459 2.31682204

H 3.65478554 -3.44259873 0.83261331

C 0.89831764 -3.22978876 2.79882363

H -0.71249803 -1.82386403 2.57651491

H 2.63779958 -4.52517522 2.80699129

H 0.44660698 -3.70582388 3.67403286

C -1.72035469 0.07933387 1.04722001

C -2.76313413 -0.76101290 0.56881686

C -2.01025266 0.87257612 2.17113445

C -4.02037491 -0.79383502 1.19368759

C -2.43582629 -1.59048558 -0.58889316

C -3.25751526 0.83538180 2.78746398

H -1.23410642 1.52839366 2.57249446

C -4.27126073 0.00210869 2.30157161

H -4.81180920 -1.44586060 0.81528272

C -3.29617560 -2.51740929 -1.19724703

H -3.44731484 1.46422538 3.66217358

H -5.24881003 -0.02406750 2.78811438

C -0.75837785 -2.14128396 -2.11906742

C -2.86048279 -3.25738595 -2.28544733

H -4.30328496 -2.65589425 -0.80436165

C -1.56140370 -3.07140479 -2.76199645

H 0.27022263 -1.95736074 -2.43892538

H -3.52729093 -3.98185076 -2.75888376

H -1.17316801 -3.63790053 -3.60937499

N -1.18202102 -1.42059810 -1.07683756

C -0.15520348 2.90563657 -0.58971088

C -1.46338895 1.72871866 -2.12679953

C -0.52211987 4.11414752 -1.20165791

C 0.72001848 2.77388462 0.57312738

C -1.86121725 2.88919512 -2.77366419

H -1.81791319 0.74611096 -2.44764729

C -1.37377275 4.10694585 -2.29536844

H -0.13934280 5.05543436 -0.80755998

C 0.92315032 1.45037015 1.05224777

C 1.31701199 3.87857243 1.20194236

H -2.54044030 2.83638038 -3.62545723

H -1.66304625 5.04659184 -2.77183207

C 1.74847348 1.30397901 2.18095829

C 2.12513377 3.69714085 2.31457434

H 1.15050564 4.89023888 0.82308669

C 2.33662182 2.40226678 2.80117156

H 1.92559465 0.30363467 2.58285826

H 2.58863363 4.55643063 2.80428368

H 2.97087444 2.25159426 3.67958431

N -0.63391888 1.73510439 -1.07938881

N 1.82331270 -0.31615001 -1.07209969

C 0.78888390 -1.52564414 1.05342887

End Geometry

Basis

Def2-SVP

Skeleton

Group

C(1)

$end

$bdfopt

Solver

1

MaxCycle

366

IOpt

3

Hess

final

$end

$xuanyuan

Direct

$end

$scf

RKS

Charge

0

SpinMulti

1

DFT

PBE0

D3

Molden

$end

$tddft

Imethod

1

Isf

1

Ialda

4

Idiag

1

crit_e

1E-9

crit_vec

1E-7

Gridtol

1E-6

Iroot

6

Istore

1

$end

$resp

Geom

Method

2

Nfiles

1

Iroot

1

$end

选中bdf.inp文件，右击选择Run提交作业，任务结束后bdf.out，bdf.out.tmp，bdf.scf.molden三个结果文件会出现在Project中。

选择bdf.out，右击show view，在Optimization对话框中，显示结构已经达到收敛标准。

在Frequency对话框中，检查频率，若不存在虚频证明结构已经优化到极小点。

选择bdf.out文件，右击open with containing folder打开bdf.out文件，在文件中查找‘converged in’，紧接着输出的‘Molecular Cartesian Coordinates (X,Y,Z) in Angstrom : ’下的结构即为优化好的T1激发态的结构。将其保存为Irppy3_t1_soc.xyz文件，如下：

61

Ir          0.00713728       0.02772384       0.06844143

C           2.49525480      -1.44901550      -0.61634342

C           2.18832036       0.30085414      -2.14613716

C           3.68634391      -1.80881598      -1.26572189

C           1.93194560      -2.11689508       0.55823360

C           3.35838993      -0.00562745      -2.82371008

H           1.54555778       1.13535499      -2.43828057

C           4.11644204      -1.08671357      -2.36826138

H           4.27131595      -2.65056635      -0.89578008

C           2.53568350      -3.23676194       1.15281696

H           3.66807720       0.59265321      -3.68133338

H           5.04582829      -1.36185464      -2.87261245

C           0.15985754      -2.20796739       2.19060975

C           1.95468524      -3.83725789       2.26057143

H           3.46642195      -3.64596143       0.75209976

C           0.76249168      -3.31842903       2.77624738

H          -0.76777546      -1.81381956       2.61329026

H           2.42616559      -4.70662836       2.72403491

H           0.30108846      -3.78788395       3.64972556

C          -1.72817262       0.21988877       1.05055833

C          -2.80684294      -0.57231379       0.57552059

C          -1.98377974       1.07446425       2.13652018

C          -4.07348284      -0.50293868       1.17614116

C          -2.51722058      -1.44616477      -0.55935718

C          -3.24105830       1.13344573       2.72846833

H          -1.17254968       1.69178400       2.52835606

C          -4.29332764       0.34509124       2.25152759

H          -4.89835192      -1.11318656       0.80076906

C          -3.42583031      -2.33456216      -1.15446766

H          -3.40666531       1.80444609       3.57586126

H          -5.27935386       0.39610056       2.71819787

C          -0.85701735      -2.13799807      -2.04878703

C          -3.02057249      -3.12865177      -2.21547404

H          -4.44525951      -2.39959512      -0.77498376

C          -1.70631730      -3.03592702      -2.67708276

H           0.18295061      -2.02278722      -2.36320871

H          -3.72428268      -3.82273458      -2.68079360

H          -1.34337957      -3.64618311      -3.50492143

N          -1.25281509      -1.36491844      -1.03498749

C           0.05749757       2.91146589      -0.57266019

C          -1.32777267       1.80183369      -2.13392316

C          -0.20378718       4.13789922      -1.23242993

C           0.84833732       2.74053836       0.60027468

C          -1.62207961       2.97568834      -2.79963589

H          -1.76529075       0.85235254      -2.45705604

C          -1.02279372       4.18710974      -2.33345871

H           0.25619858       5.05119986      -0.85064151

C           0.99228869       1.37116718       1.10523883

C           1.50408647       3.78492492       1.29091761

H          -2.29824567       2.96275979      -3.65460398

H          -1.21968527       5.13470890      -2.83803374

C           1.79964051       1.14876808       2.23660071

C           2.27478596       3.51131149       2.40946143

H           1.40861651       4.81693356       0.94742301

C           2.43450283       2.19478112       2.89597173

H           1.90681895       0.12796182       2.60984200

H           2.77105979       4.33756352       2.92655136

H           3.04508360       2.00761950       3.78145403

N          -0.50508694       1.73366277      -1.08285478

N           1.77567220      -0.40171722      -1.08777429

C           0.72548984      -1.57229627       1.07484739

下一期将介绍使用BDF软件基于T1激发态结构，做S0和T1之间的旋轨耦合SOC计算，以及基于BDF的量化计算结果，使用MOMAP软件进行Ir(ppy)3的磷光辐射速率计算的过程。

编辑：黄飞