Hello,
We are currently trying to perform SOC computation with the TD-DFT method but with a triplet ground state. Here is the relevant input for the Si17H36 molecule:
$molecule
0 3
Si 4.565393568581 -3.816245866555 5.990644702250
Si 3.715364211679 -5.801154961144 5.089950779278
Si 2.226464673811 3.826347417073 -1.276591968872
Si 0.533512423306 2.927148468449 -2.654709961282
Si 1.720565928981 1.643844904805 -4.240474917713
Si 4.788263741870 -6.611619522210 3.175342851592
Si -1.388209882214 4.902940846827 0.942260662361
Si -2.371687978534 2.920665358924 0.120741521407
Si -2.803610397138 1.658144688051 2.068499291880
Si 2.990185118353 -7.407803537822 6.628269725755
Si -0.520922178516 4.672605195735 -3.847435178496
Si -4.418324225520 3.545789847515 -0.880252986201
Si -1.006205314266 1.695810610037 -1.361119034378
Si -2.964897459008 0.327708763241 -4.455648408618
Si -0.347501374067 -1.883732402407 -2.688212353730
Si -3.638252125680 -1.258044211807 -1.082410290589
Si -1.972873004289 -0.199661053143 -2.377462345094
H 3.629824295869 -3.292088221649 7.015318174775
H 5.891375860046 -4.015053457925 6.631712127621
H 4.717764974383 -2.805073734483 4.916275188529
H 1.689351207448 4.771104542081 -0.269871770134
H 2.932399217250 2.731402883087 -0.567113598649
H 3.208040143124 4.552104166118 -2.121521209486
H 0.822290739155 0.961182773262 -5.200646114645
H 2.599664296434 2.569966157775 -4.997966376863
H 2.572924210751 0.630334999468 -3.574142812025
H 3.978780395982 -7.697762483907 2.571182360423
H 4.938908607136 -5.516789281168 2.186083132653
H 6.139033648735 -7.152972257180 3.477159773743
H -1.002009968763 5.833849204438 -0.143543685508
H -2.393113073652 5.577130478411 1.802493725150
H -0.193289926457 4.602825815606 1.766765720897
H -3.551057512201 0.412605401862 1.777575736216
H -1.525161697788 1.297912529132 2.729118627498
H -3.608282830942 2.476350100854 3.010397857086
H 2.235178183410 -8.471081246576 5.921580466099
H 4.123293658870 -8.044569631435 7.348913099747
H 2.101575296780 -6.772995938046 7.631951746334
H -1.487824314943 4.109047355641 -4.821007148452
H -1.250095928509 5.580863036682 -2.930978267864
H 0.491887526048 5.464192755053 -4.590830611706
H -5.149691296758 2.360073486518 -1.385933886159
H -5.275964052154 4.242908572555 0.111457974723
H -4.167342802471 4.465340337599 -2.016834903731
H -3.489951466751 -0.905292862752 -5.095221893970
H -4.091031884163 1.271969875412 -4.254577366777
H -1.983066466057 0.953692601419 -5.372505558250
H -0.999568965113 -3.088676839998 -3.260122172834
H 0.734521923757 -1.459471706889 -3.606798798433
H 0.256840574148 -2.248285613910 -1.383434021800
H -4.179387760370 -2.384856150508 -1.883508192523
H -3.068828830530 -1.807102195382 0.171413096670
H -4.755251706653 -0.345530008307 -0.744232509010
$end
$rem
MEM_TOTAL 8000
MEM_STATIC 200
JOBTYPE sp
EXCHANGE b3lyp
BASIS def2-svp
SCF_ALGORITHM diis
MAX_SCF_CYCLES 100
CIS_N_ROOTS 5
CIS_SINGLETS true
CIS_TRIPLETS true
STS_MOM true
CALC_SOC true
IQMOL_FCHK True
$end
The output seems rather weird though. Only 5 states have been computed with no information about their multiplicity instead of the 5 singlets and 5 triplets we were expecting:
Direct TDDFT/TDA calculation will be performed
Exchange: 0.2000 Hartree-Fock + 0.0800 Slater + 0.7200 B88
Correlation: 0.1900 VWN1RPA + 0.8100 LYP
Using SG-1 standard quadrature grid
CIS energy converged when residual is below 10e- 6
---------------------------------------------------
Iter Rts Conv Rts Left Ttl Dev Max Dev
---------------------------------------------------
1 0 5 0.000365 0.000141
2 2 3 0.000134 0.000046
3 2 3 0.000053 0.000019
4 2 3 0.000024 0.000009
5 2 3 0.000011 0.000004
6 0 5 0.000199 0.000098
7 3 2 0.000142 0.000070
8 3 2 0.000054 0.000027
9 3 2 0.000019 0.000009
10 3 2 0.000013 0.000006
11 3 2 0.000011 0.000005
12 3 2 0.000006 0.000003
13 5 0 0.000003 0.000001 Roots Converged
---------------------------------------------------
---------------------------------------------------
TDDFT/TDA Excitation Energies
---------------------------------------------------
Excited state 1: excitation energy (eV) = 3.0143
Total energy for state 1: -4941.62726973 au
<S**2> : 2.0245
Trans. Mom.: -0.0432 X 0.0312 Y -0.1381 Z
Strength : 0.0016183467
D( 136) --> S( 1) amplitude = 0.9799 beta
Excited state 2: excitation energy (eV) = 3.0155
Total energy for state 2: -4941.62722621 au
<S**2> : 2.0245
Trans. Mom.: -0.0191 X -0.1450 Y -0.0257 Z
Strength : 0.0016298610
D( 135) --> S( 1) amplitude = 0.9799 beta
Excited state 3: excitation energy (eV) = 3.2014
Total energy for state 3: -4941.62039347 au
<S**2> : 2.0240
Trans. Mom.: -0.1229 X 0.0095 Y 0.0406 Z
Strength : 0.0013217838
S( 2) --> V( 1) amplitude = 0.9898 alpha
Excited state 4: excitation energy (eV) = 3.5809
Total energy for state 4: -4941.60644691 au
<S**2> : 2.0244
Trans. Mom.: -0.0468 X 0.1468 Y -0.1788 Z
Strength : 0.0048872767
S( 2) --> V( 2) amplitude = -0.9662 alpha
S( 2) --> V( 3) amplitude = 0.1511 alpha
Excited state 5: excitation energy (eV) = 3.5817
Total energy for state 5: -4941.60641768 au
<S**2> : 2.0244
Trans. Mom.: -0.0630 X -0.1826 Y -0.1377 Z
Strength : 0.0049392705
S( 2) --> V( 2) amplitude = 0.1512 alpha
S( 2) --> V( 3) amplitude = 0.9660 alpha
---------------------------------------------------
SETman timing summary (seconds)
CPU time 1590.58s
System time 0.00s
Wall time 207.14s
On top of that, the SOC results section mentions a singlet ground state as well as the usual 5 triplet and 5 singlet excited states:
=======================================================================================
SPIN-ORBIT COUPLING BETWEEN THE SINGLET GROUND STATE AND EXCITED TRIPLET STATE
=======================================================================================
SOC between the singlet ground state and excited triplet states (ms=0):
T1(ms=0) 0.000000 + -0.868171i cm-1
T2(ms=0) 0.000000 + 7.229184i cm-1
T3(ms=0) 0.000000 + 0.753279i cm-1
T4(ms=0) 0.000000 + -15.820413i cm-1
T5(ms=0) 0.000000 + 40.114332i cm-1
SOC between the singlet ground state and excited triplet states (ms=1):
T1(ms=1) -5.348454 + (-0.620998i) cm-1
T2(ms=1) -0.781414 + (1.631144i) cm-1
T3(ms=1) 0.119509 + (-1.432836i) cm-1
T4(ms=1) -29.475830 + (-6.004400i) cm-1
T5(ms=1) -12.466265 + (8.382454i) cm-1
SOC between the singlet ground state and excited triplet states (ms=-1):
T1(ms=-1) -5.348454 - (-0.620998i) cm-1
T2(ms=-1) -0.781414 - (1.631144i) cm-1
T3(ms=-1) 0.119509 - (-1.432836i) cm-1
T4(ms=-1) -29.475830 - (-6.004400i) cm-1
T5(ms=-1) -12.466265 - (8.382454i) cm-1
Total SOC between the singlet ground state and excited triplet states:
T1 7.664002 cm-1
T2 7.668349 cm-1
T3 2.168417 cm-1
T4 45.387666 cm-1
T5 45.392800 cm-1
=======================================================================================
SPIN-ORBIT COUPLING BETWEEN EXCITED TRIPLET STATES
=======================================================================================
SOC between the T1 (ms=0) state and excited triplet states (ms=1):
T2(ms=1) 0.034530 + (-0.436316i) cm-1
T3(ms=1) 1.296887 + (-0.030390i) cm-1
T4(ms=1) 0.481655 + (1.528259i) cm-1
T5(ms=1) -0.455493 + (-2.799411i) cm-1
SOC between the T1 (ms=0) state and excited triplet states (ms=-1):
T2(ms=-1) -0.034530 + (-0.436316i) cm-1
T3(ms=-1) -1.296887 + (-0.030390i) cm-1
T4(ms=-1) -0.481655 + (1.528259i) cm-1
T5(ms=-1) 0.455493 + (-2.799411i) cm-1
SOC between the T1 (ms=1) state and excited triplet states (ms=0):
T2(ms=0) -0.034530 + (-0.436316i) cm-1
T3(ms=0) -1.296887 + (-0.030390i) cm-1
T4(ms=0) -0.481655 + (1.528259i) cm-1
T5(ms=0) 0.455493 + (-2.799411i) cm-1
SOC between the T1 (ms=1) state and excited triplet states (ms=1):
T2(ms=1) 0.000000 + (0.204354i) cm-1
T3(ms=1) 0.000000 + (-0.533557i) cm-1
T4(ms=1) 0.000000 + (0.300910i) cm-1
T5(ms=1) 0.000000 + (2.172311i) cm-1
SOC between the T1 (ms=-1) state and excited triplet states (ms=0):
T2(ms=0) 0.034530 + (-0.436316i) cm-1
T3(ms=0) 1.296887 + (-0.030390i) cm-1
T4(ms=0) 0.481655 + (1.528259i) cm-1
T5(ms=0) -0.455493 + (-2.799411i) cm-1
SOC between the T1 (ms=-1) state and excited triplet states (ms=-1):
T2(ms=-1) 0.000000 + (-0.204354i) cm-1
T3(ms=-1) 0.000000 + (0.533557i) cm-1
T4(ms=-1) 0.000000 + (-0.300910i) cm-1
T5(ms=-1) 0.000000 + (-2.172311i) cm-1
Total SOC between the T1 state and excited triplet states:
T2 0.921834 cm-1
T3 2.701986 cm-1
T4 3.232858 cm-1
T5 6.450936 cm-1
SOC between the T2 (ms=0) state and excited triplet states (ms=1):
T3(ms=1) -0.371124 + (-0.434865i) cm-1
T4(ms=1) -0.910824 + (3.068900i) cm-1
T5(ms=1) -0.672726 + (1.022898i) cm-1
SOC between the T2 (ms=0) state and excited triplet states (ms=-1):
T3(ms=-1) 0.371124 + (-0.434865i) cm-1
T4(ms=-1) 0.910824 + (3.068900i) cm-1
T5(ms=-1) 0.672726 + (1.022898i) cm-1
SOC between the T2 (ms=1) state and excited triplet states (ms=0):
T3(ms=0) 0.371124 + (-0.434865i) cm-1
T4(ms=0) 0.910824 + (3.068900i) cm-1
T5(ms=0) 0.672726 + (1.022898i) cm-1
SOC between the T2 (ms=1) state and excited triplet states (ms=1):
T3(ms=1) 0.000000 + (-1.742617i) cm-1
T4(ms=1) 0.000000 + (-0.579546i) cm-1
T5(ms=1) 0.000000 + (-1.480097i) cm-1
SOC between the T2 (ms=-1) state and excited triplet states (ms=0):
T3(ms=0) -0.371124 + (-0.434865i) cm-1
T4(ms=0) -0.910824 + (3.068900i) cm-1
T5(ms=0) -0.672726 + (1.022898i) cm-1
SOC between the T2 (ms=-1) state and excited triplet states (ms=-1):
T3(ms=-1) 0.000000 + (1.742617i) cm-1
T4(ms=-1) 0.000000 + (0.579546i) cm-1
T5(ms=-1) 0.000000 + (1.480097i) cm-1
Total SOC between the T2 state and excited triplet states:
T3 2.716761 cm-1
T4 6.454668 cm-1
T5 3.221320 cm-1
SOC between the T3 (ms=0) state and excited triplet states (ms=1):
T4(ms=1) -10.790625 + (-1.527163i) cm-1
T5(ms=1) -2.677706 + (3.223598i) cm-1
SOC between the T3 (ms=0) state and excited triplet states (ms=-1):
T4(ms=-1) 10.790625 + (-1.527163i) cm-1
T5(ms=-1) 2.677706 + (3.223598i) cm-1
SOC between the T3 (ms=1) state and excited triplet states (ms=0):
T4(ms=0) 10.790625 + (-1.527163i) cm-1
T5(ms=0) 2.677706 + (3.223598i) cm-1
SOC between the T3 (ms=1) state and excited triplet states (ms=1):
T4(ms=1) 0.000000 + (-3.240925i) cm-1
T5(ms=1) 0.000000 + (14.578591i) cm-1
SOC between the T3 (ms=-1) state and excited triplet states (ms=0):
T4(ms=0) -10.790625 + (-1.527163i) cm-1
T5(ms=0) -2.677706 + (3.223598i) cm-1
SOC between the T3 (ms=-1) state and excited triplet states (ms=-1):
T4(ms=-1) 0.000000 + (3.240925i) cm-1
T5(ms=-1) 0.000000 + (-14.578591i) cm-1
Total SOC between the T3 state and excited triplet states:
T4 22.272999 cm-1
T5 22.255727 cm-1
SOC between the T4 (ms=0) state and excited triplet states (ms=1):
T5(ms=1) 2.055651 + (-27.803903i) cm-1
SOC between the T4 (ms=0) state and excited triplet states (ms=-1):
T5(ms=-1) -2.055651 + (-27.803903i) cm-1
SOC between the T4 (ms=1) state and excited triplet states (ms=0):
T5(ms=0) -2.055651 + (-27.803903i) cm-1
SOC between the T4 (ms=1) state and excited triplet states (ms=1):
T5(ms=1) 0.000000 + (12.977354i) cm-1
SOC between the T4 (ms=-1) state and excited triplet states (ms=0):
T5(ms=0) 2.055651 + (-27.803903i) cm-1
SOC between the T4 (ms=-1) state and excited triplet states (ms=-1):
T5(ms=-1) 0.000000 + (-12.977354i) cm-1
Total SOC between the T4 state and excited triplet states:
T5 58.702251 cm-1
=======================================================================================
SPIN-ORBIT COUPLING BETWEEN EXCITED SINGLET STATES AND TRIPLET STATES
=======================================================================================
SOC between the S1 state and excited triplet states (ms=0):
T1(ms=0) 0.000000 + -56.659477i cm-1
T2(ms=0) 0.000000 + 42.781833i cm-1
T3(ms=0) 0.000000 + 1493.109352i cm-1
T4(ms=0) 0.000000 + -8.858243i cm-1
T5(ms=0) 0.000000 + 543.068930i cm-1
SOC between the S1 state and excited triplet states (ms=1):
T1(ms=1) (59.329289) + (96.344346i) cm-1
T2(ms=1) (-74.008877) + (-32.065249i) cm-1
T3(ms=1) (2527.113936) + (-234.019029i) cm-1
T4(ms=1) (875.541078) + (1143.586386i) cm-1
T5(ms=1) (-121.083032) + (78.645564i) cm-1
SOC between the S1 state and excited triplet states (ms=-1):
T1(ms=-1) -(59.329289) + (96.344346i) cm-1
T2(ms=-1) -(-74.008877) + (-32.065249i) cm-1
T3(ms=-1) -(2527.113936) + (-234.019029i) cm-1
T4(ms=-1) -(875.541078) + (1143.586386i) cm-1
T5(ms=-1) -(-121.083032) + (78.645564i) cm-1
Total SOC between the S1 state and excited triplet states:
T1 169.748907 cm-1
T2 121.824764 cm-1
T3 3887.353218 cm-1
T4 2036.860935 cm-1
T5 580.186447 cm-1
SOC between the S2 state and excited triplet states (ms=0):
T1(ms=0) 0.000000 + 580.679793i cm-1
T2(ms=0) 0.000000 + 145.807004i cm-1
T3(ms=0) 0.000000 + 4028.593601i cm-1
T4(ms=0) 0.000000 + 2984.376246i cm-1
T5(ms=0) 0.000000 + 4517.408835i cm-1
SOC between the S2 state and excited triplet states (ms=1):
T1(ms=1) (-217.979192) + (-15.281831i) cm-1
T2(ms=1) (119.665658) + (-42.321260i) cm-1
T3(ms=1) (2530.462315) + (-69.709131i) cm-1
T4(ms=1) (-3317.881746) + (-410.606102i) cm-1
T5(ms=1) (230.375815) + (-633.405052i) cm-1
SOC between the S2 state and excited triplet states (ms=-1):
T1(ms=-1) -(-217.979192) + (-15.281831i) cm-1
T2(ms=-1) -(119.665658) + (-42.321260i) cm-1
T3(ms=-1) -(2530.462315) + (-69.709131i) cm-1
T4(ms=-1) -(-3317.881746) + (-410.606102i) cm-1
T5(ms=-1) -(230.375815) + (-633.405052i) cm-1
Total SOC between the S2 state and excited triplet states:
T1 657.788680 cm-1
T2 231.260892 cm-1
T3 5389.412231 cm-1
T4 5591.097825 cm-1
T5 4616.874758 cm-1
SOC between the S3 state and excited triplet states (ms=0):
T1(ms=0) 0.000000 + -15.454128i cm-1
T2(ms=0) 0.000000 + 75.941387i cm-1
T3(ms=0) 0.000000 + 117.840024i cm-1
T4(ms=0) 0.000000 + -291.642814i cm-1
T5(ms=0) 0.000000 + 404.329379i cm-1
SOC between the S3 state and excited triplet states (ms=1):
T1(ms=1) (191.354980) + (19.459601i) cm-1
T2(ms=1) (212.198388) + (-15.474412i) cm-1
T3(ms=1) (-782.562538) + (-400.317989i) cm-1
T4(ms=1) (-750.661399) + (655.131050i) cm-1
T5(ms=1) (651.265325) + (-61.137335i) cm-1
SOC between the S3 state and excited triplet states (ms=-1):
T1(ms=-1) -(191.354980) + (19.459601i) cm-1
T2(ms=-1) -(212.198388) + (-15.474412i) cm-1
T3(ms=-1) -(-782.562538) + (-400.317989i) cm-1
T4(ms=-1) -(-750.661399) + (655.131050i) cm-1
T5(ms=-1) -(651.265325) + (-61.137335i) cm-1
Total SOC between the S3 state and excited triplet states:
T1 272.451168 cm-1
T2 310.326152 cm-1
T3 1248.680707 cm-1
T4 1438.900271 cm-1
T5 1009.579537 cm-1
SOC between the S4 state and excited triplet states (ms=0):
T1(ms=0) 0.000000 + -469.758518i cm-1
T2(ms=0) 0.000000 + -200.118790i cm-1
T3(ms=0) 0.000000 + -117.217263i cm-1
T4(ms=0) 0.000000 + -771.627013i cm-1
T5(ms=0) 0.000000 + 2399.756612i cm-1
SOC between the S4 state and excited triplet states (ms=1):
T1(ms=1) (-43.251288) + (62.646067i) cm-1
T2(ms=1) (-159.913351) + (-61.825560i) cm-1
T3(ms=1) (1918.387972) + (-599.643933i) cm-1
T4(ms=1) (-2679.518534) + (2156.726787i) cm-1
T5(ms=1) (-553.453193) + (752.108116i) cm-1
SOC between the S4 state and excited triplet states (ms=-1):
T1(ms=-1) -(-43.251288) + (62.646067i) cm-1
T2(ms=-1) -(-159.913351) + (-61.825560i) cm-1
T3(ms=-1) -(1918.387972) + (-599.643933i) cm-1
T4(ms=-1) -(-2679.518534) + (2156.726787i) cm-1
T5(ms=-1) -(-553.453193) + (752.108116i) cm-1
Total SOC between the S4 state and excited triplet states:
T1 481.937208 cm-1
T2 314.383348 cm-1
T3 2844.874409 cm-1
T4 4925.239919 cm-1
T5 2739.121375 cm-1
SOC between the S5 state and excited triplet states (ms=0):
T1(ms=0) 0.000000 + -151.707114i cm-1
T2(ms=0) 0.000000 + -664.882667i cm-1
T3(ms=0) 0.000000 + -2721.119681i cm-1
T4(ms=0) 0.000000 + -492.444125i cm-1
T5(ms=0) 0.000000 + 596.019004i cm-1
SOC between the S5 state and excited triplet states (ms=1):
T1(ms=1) (-91.581712) + (-63.116183i) cm-1
T2(ms=1) (1.398841) + (-97.320193i) cm-1
T3(ms=1) (-1269.027401) + (-1857.767239i) cm-1
T4(ms=1) (-99.357495) + (-695.899219i) cm-1
T5(ms=1) (738.690940) + (-1485.437547i) cm-1
SOC between the S5 state and excited triplet states (ms=-1):
T1(ms=-1) -(-91.581712) + (-63.116183i) cm-1
T2(ms=-1) -(1.398841) + (-97.320193i) cm-1
T3(ms=-1) -(-1269.027401) + (-1857.767239i) cm-1
T4(ms=-1) -(-99.357495) + (-695.899219i) cm-1
T5(ms=-1) -(738.690940) + (-1485.437547i) cm-1
Total SOC between the S5 state and excited triplet states:
T1 218.533232 cm-1
T2 678.981086 cm-1
T3 4186.639659 cm-1
T4 1109.412676 cm-1
T5 2420.664511 cm-1
Do we need to specify some additional parameters in the input file? Are we missing something?
Thank you very much for your help!
Best regards!
Iacobellis Nicolas, Ph.D. Student
