上一期介紹了使用量化軟件BDF進行Ir(ppy)?的基態S0的結構優化和頻率計算。這一期將介紹第一激發三重態T1的結構優化和頻率計算的過程。

Irppy3_t1.xyz內容如下：

準備Ir(ppy)?分子結構的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

選擇Simulator → BDF → BDF，在界面中設置參數。在Basic Settings界面中的Calculation Type選擇TDDFT-OPT+Freq，方法采用默認的PBE0泛函，基組在Basis中的All Electron類型中，選擇Def2-SVP。Basic Settings界面中的其它參數使用推薦的默認值，不需要做修改。

SCF Settings界面中將Use MPEC+COSX Acceleraton的默認勾選去掉。SCF Settings界面中的其它參數使用推薦的默認值，不需要做修改。

TDDFT Settings面板中將Use MPEC+COSX Acceleraton的默認勾選去掉。Mutiplicity選擇Triplet，Convergence Threshold選擇Very Tight。TDDFT Settings界面中的其它參數使用推薦的默認值，不需要做修改。

OPT Settings和Freq Settings面板的參數使用推薦的默認值，不需要做修改。之后點擊 Generate files 即可生成對應計算的輸入文件。選中生成的bdf.inp文件，右擊選擇open containing folder進入所在文件夾，在bdf.inp的$tddft模塊中加入：

Gridtol

1E-6

bdf.inp內容如下：

$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

選中bdf.inp文件，右擊選擇Run提交作業，任務結束后bdf.out，bdf.out.tmp，bdf.scf.molden三個結果文件會出現在Project中。

選擇bdf.out，右擊show view，在Optimization對話框中，顯示結構已經達到收斂標準。

在Frequency對話框中，檢查頻率，若不存在虛頻證明結構已經優化到極小點。

選擇bdf.out文件，右擊open with containing folder打開bdf.out文件，在文件中查找‘converged in’，緊接著輸出的‘Molecular Cartesian Coordinates (X,Y,Z) in Angstrom : ’下的結構即為優化好的T1激發態的結構。將其保存為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

下一期將介紹使用BDF軟件基于T1激發態結構，做S0和T1之間的旋軌耦合SOC計算，以及基于BDF的量化計算結果，使用MOMAP軟件進行Ir(ppy)3的磷光輻射速率計算的過程。

編輯：黃飛