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| = TD-DFT/SOC = SOC计算的输入文件中以$section name ... $end符号为划分分为6段: . $compass 为基组和坐标控制（如果要计算其他化合物，选用其他基组，可修改这一段）； $xuanyuan 为积分控制，基本不需要改动，除非需要使用cam-b3lyp这段要加入两行：RS和0.33d0，控制计算新的积分; $scf为计算方法控制，可选用不同泛函； $tddft isf=0 ... 这一段(isf=0)表示计算singlet $tddft isf=1 ... 计算triplet $tddft isoc=2 ...根据前面两个计算的结果来计算soc state interaction，imatsoc为控制打印旋轨耦合矩阵元，格式如下： IMATSOC n fileA symA stateA fileB symB stateB fileA' symA' stateA' fileB' symB' stateB' . .. . .. n代表要打印几个态的旋轨耦合矩阵元<A|hso|B>，接着后面为要打印矩阵元两个态的描述，每个态由(file,sym,state)3个量表示，file表示前面第几个tddft的文件，sym表示该计算中第几个不可约表示，state表示该不可约表示里的第几个态。如输入文件中（0，0，0，2，1，1）表示基态和file2即triplet，sym＝1的第一个态(即T1)，之间的旋轨耦合矩阵元。 = Example = $COMPASS Title . ir1 Basis . IRCOMPLEX Geometry . Ir -0.0117154745 0.02136826 -0.1871622466 C -1.590674169 0.7736105591 0.850482009 C -4.0103593084 1.6631710744 2.0881698872 C -1.587030516 1.6064254297 1.9846531563 C -2.8754743453 0.4162567381 0.3762778017 C -4.0684588604 0.8406678872 0.9653728357 C -2.7652566303 2.0433988261 2.5945234724 H -0.633533598 1.9127046365 2.4024890794 H -5.031807216 0.5389051931 0.5644872718 H -2.7118027246 2.6839610147 3.4712663621 H -4.9285536031 2.0014173162 2.5588819363 C 1.4053272337 1.0109349589 0.8613594531 C 3.3836289249 2.6234305864 2.1354680771 C 2.0771460677 0.5800974992 2.0211645669 C 1.7631262545 2.2970140474 0.3585152663 C 2.7411852479 3.0844966855 0.9939992732 C 3.044957901 1.3650101996 2.6469305081 H 1.8305785647 -0.3881315485 2.4444240781 H 3.0042061929 4.0630294704 0.6010854425 H 3.5407187868 0.9959817385 3.5420383099 H 4.1379887938 3.2338708527 2.6233130653 C 0.1111675725 -1.7119838156 0.8795182027 C 0.5294631611 -4.2465845213 2.136544371 C 1.0417183334 -2.6652412426 0.4024936912 C -0.6004107662 -2.1019903883 2.028797446 C -0.4006210626 -3.3384592866 2.6477946425 C 1.2608503358 -3.9079720636 1.0002003463 H -1.3244348019 -1.413608967 2.4531282601 H -0.9731808696 -3.5946754614 3.5357463104 H 1.9890357565 -4.6057356294 0.596753782 H 0.6876544671 -5.2085686031 2.6147222734 N -1.7055918832 -0.7893527004 -1.3058124454 C -1.9722242221 -1.5767164653 -2.3518797181 C -3.3612772292 -1.7339951323 -2.5010242321 C -3.9194938069 -0.9920736156 -1.4729787184 N -2.8999954385 -0.434228237 -0.7703095731 N 1.5150714233 -1.0583114657 -1.2825131804 C 2.3138081406 -0.9142123699 -2.3433358371 C 3.1082799478 -2.0614459074 -2.5127910698 C 2.7399679653 -2.9098550697 -1.4816601802 N 1.779892419 -2.2802990117 -0.7566347846 H -1.1601491745 -1.9907288667 -2.9313421992 H 3.089224611 -3.8952971699 -1.2184247348 H 3.8501674705 -2.2464169166 -3.2743336863 H -3.8863865729 -2.3105313491 -3.2470045506 H -4.9492341453 -0.8290099882 -1.1983109053 H 2.2814545468 -0.0015798294 -2.9198044757 C 0.5167706643 4.2876200227 -2.6332627231 C -0.4153270812 3.3663568698 -3.1195481682 C -0.5686406908 2.1688169354 -2.4341135463 N 0.1409383672 1.8631654694 -1.3352631181 C 1.05542065 2.7471949823 -0.8428699526 C 1.2493629941 3.9769776219 -1.4963443658 H 0.6676353447 5.2385692731 -3.1359337322 H -1.011339893 3.5685529446 -4.0026032407 H -1.276466123 1.413706092 -2.7596936709 H 1.9731120675 4.6831024371 -1.1074561222 End geometry GROUP C(1) Skeleton $END $XUANYUAN scalar heff 3 soint hsoc 2 Direct Schwarz $END $SCF RKS DFT functional . B3lyp |
##master-page:HelpTemplate ##master-date:Unknown-Date #format wiki #language en #Please change following line to BDF module name = tddft: time-dependent density functional theory = <<TableOfContents(4)>> {{{ Time dependent DFT/HF calculation. Support Full TDDFT, TDA and RPA. }}} == Quick guides == The following examples give the minimal inputs for starting TD-DFT calculations. 1. [[Closed-shell Systems : R-TD-DFT]] 2. [[Open-shell Systems : U-TD-DFT and spin-adapted TD-DFT for spin-conserving excitations]] 3. [[Open-shell Systems : Spin-flip TD-DFT for spin-flip excitations]] 4. [[TD-DFT with SOC]] 5. [[TD-DFT with SOC: Kramers pairs]] 6. [[Excitation analyze based on molecular fragments]] == General keywords == === imethod === {{{ imethod 1, R-TDDFT, start from RKS imethod 2, U-TDDFT, start from UKS or ROKS imethod 3, X-TDDFT, start from ROKS }}} === isf === {{{ Spin flip TDDFT. isf 0, do not flip isf 1, spin flip up isf -1, spin flip down }}} === itda === {{{ itda 0, TDDFT, do not use TDA itda 1, TDA }}} === idrpa === === ispa === === ialda === === thrdab === === itest === === icorrect === === itrans === === iro === === icv === === ioo === === iksf === === iact === iact = 1: define active space based on energy [elw,eup] === elw === lower bound in eV (not in au!). === eup === upper bound in eV. === idiag === === ndiag === === aokxc === == Convergence threshold == === crit_e === === crit_vec === == States specification == === iexit === {{{ The number of calculated excited states of each irreducible representation for a specific point group }}} === nexit === {{{ Same as above }}} == Save eigenvectors == === istore === Integer: specify the file no. to store TDDFT information === lefteig === By default, in TD-DFT the left eigenvector X-Y is also stored. == output eigenvector control == === nprt === === cthrd === == TD-DFT/SOC and Property evaluation == === nfiles === No. of TD-DFT calculations to be loaded. === isoc === =1, Only work for closed-shell case (NOT recommended!) =2, General SOC state interaction =3, just print SOC matrix elements between two spin-free states (without diagonalization Hsoc). === ifgs === =0, default for not including ground state (GS) in SOC treatment; =1, include GS. === imatsoc === Define SOC matrices need to be calculated. Input format looks like {{{ ... #SCF calculation for the ground state S0. It is a singlet. $scf spin 0 ... $end #First TDDFT, singlets S0-S9. $tddft imethod 1 isf 0 iext 10 .... $end #Second TDDFT, triplet T1-T10 $tddft imethod 1 isf 1 iexit 10 $end $tddft .... imatsoc 7 0 0 0 2 1 1 0 0 0 2 1 2 1 1 1 2 1 1 1 1 1 2 1 2 1 1 2 2 1 1 1 1 2 2 1 2 2 1 1 2 1 1 2 1 1 2 1 2 $end }}} In this input, 7 means seven of SOC matrices will be calculate '''(If the number <0, then ALL possible HSOC mat will be printed !). '''Here, it is very tricky to specify states: * The string "0 0 0" always treat as the ground state. * For other states, three numbers "n m n" represent "ith-tddft", "symmetry" and "ithstate" respectively. Therefore, the first matrix element "0 0 0 2 1 1" means SOC matrix of <S0|HSOC|T1>. The third matrix element "1 1 1 2 1 1" means SOC matrix <S1|HSOC|T1>. Here, the first "1" in bra state "1 1 1" means the state from first TDDFT calculation. The second and third "1" in the bra state "1 1 1" means this state has spatial symmetry "1" and is the first excited state. === imatrsf === Transition dipole between Spin-free states. The input is similar to '''imatsoc''' (but currently selected printing is not implemented). Simply use -1 to print all of them. === imatrso === Define transition dipole moment need to be printed between two SOC-included states. Input format looks like(notice we omit other input in TDDFT module) {{{ $TDDFT ... imatrso 5 1 1 1 2 1 3 1 4 1 5 ... |
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$TDDFT IMETHOD . 1 ISF . 0 ITDA . 0 IDIAG . 1 istore . 1 iexit 10 AOKXC MemJKOP . 2048 crit_e 1.d-4 $END $TDDFT IMETHOD . 1 ISF . 1 ITDA . 0 IDIAG . 1 istore . 2 iexit 10 AOKXC MemJKOP . 2048 crit_e 1.d-4 $END $TDDFT isoc 2 nfiles 2 ifgs 1 imatsoc 1 0 0 0 2 1 1 $END = Output = * ** List of SOC-SI results *** Totol No. of States: 41 . No. ExEnergies f Dominant Excitations Esf dE Eex(eV) (cm^-1) . 1 -0.0066 eV 0.0000 99.8% Spin: |Gs,1> 0-th A 0.0000 -0.0066 0.0000 0.00 2 2.5694 eV 0.0000 44.1% Spin: |S+,2> 1-th A 2.6425 -0.0731 2.5760 20776.65 3 2.5727 eV 0.0000 32.8% Spin: |S+,3> 1-th A 2.6425 -0.0698 2.5793 20803.69 4 2.5908 eV 0.0000 31.8% Spin: |S+,1> 1-th A 2.6425 -0.0517 2.5974 20949.77 5 2.7010 eV 0.0000 31.1% Spin: |So,1> 1-th A 2.9592 -0.2583 2.7076 21837.87 6 2.8740 eV 0.0000 19.9% Spin: |S+,1> 2-th A 2.9081 -0.0340 2.8806 23233.61 7 2.8794 eV 0.0000 27.0% Spin: |S+,2> 2-th A 2.9081 -0.0287 2.8859 23276.69 8 2.9589 eV 0.0000 22.8% Spin: |S+,1> 3-th A 2.9849 -0.0261 2.9655 23917.99 9 3.0395 eV 0.0000 26.0% Spin: |S+,2> 2-th A 2.9081 0.1314 3.0461 24568.13 . 10 3.0631 eV 0.0000 38.7% Spin: |S+,2> 3-th A 2.9849 0.0782 3.0697 24758.84 11 3.0881 eV 0.0000 52.9% Spin: |So,1> 2-th A 3.0330 0.0551 3.0947 24960.28 12 3.1239 eV 0.0000 30.7% Spin: |So,1> 1-th A 2.9592 0.1647 3.1305 25249.42 13 3.1328 eV 0.0000 21.9% Spin: |S+,2> 5-th A 3.1710 -0.0382 3.1394 25320.98 14 3.1334 eV 0.0000 20.5% Spin: |S+,3> 4-th A 3.1640 -0.0305 3.1400 25325.94 15 3.1455 eV 0.0000 33.3% Spin: |S+,2> 4-th A 3.1640 -0.0185 3.1521 25423.24 16 3.1489 eV 0.0000 24.5% Spin: |S+,2> 5-th A 3.1710 -0.0221 3.1555 25450.64 17 3.1546 eV 0.0000 17.0% Spin: |S+,3> 4-th A 3.1640 -0.0094 3.1612 25496.52 18 3.1580 eV 0.0000 34.2% Spin: |S+,3> 5-th A 3.1710 -0.0130 3.1646 25524.02 19 3.1866 eV 0.0000 17.4% Spin: |S+,2> 7-th A 3.2865 -0.1000 3.1932 25754.60 20 3.2140 eV 0.0000 28.2% Spin: |S+,3> 6-th A 3.2065 0.0074 3.2206 25975.68 21 3.2174 eV 0.0000 48.4% Spin: |S+,2> 6-th A 3.2065 0.0109 3.2240 26003.33 22 3.2435 eV 0.0000 38.0% Spin: |So,1> 3-th A 3.2231 0.0204 3.2501 26213.63 23 3.2627 eV 0.0000 20.7% Spin: |S+,3> 6-th A 3.2065 0.0562 3.2693 26368.83 24 3.2725 eV 0.0000 30.0% Spin: |S+,2> 7-th A 3.2865 -0.0140 3.2791 26447.54 25 3.3035 eV 0.0000 45.4% Spin: |So,1> 3-th A 3.2231 0.0804 3.3101 26697.85 26 3.3651 eV 0.0000 23.9% Spin: |So,1> 4-th A 3.5132 -0.1481 3.3717 27194.63 27 3.3945 eV 0.0000 31.5% Spin: |S+,1> 8-th A 3.4260 -0.0315 3.4011 27431.99 28 3.4070 eV 0.0000 31.1% Spin: |S+,1> 9-th A 3.4454 -0.0384 3.4136 27532.74 29 3.4308 eV 0.0000 31.7% Spin: |S+,3> 8-th A 3.4260 0.0047 3.4374 27724.20 30 3.4465 eV 0.0000 19.7% Spin: |S+,2> 8-th A 3.4260 0.0204 3.4531 27850.76 31 3.4518 eV 0.0000 55.5% Spin: |S+,2> 8-th A 3.4260 0.0257 3.4583 27893.46 32 3.4658 eV 0.0000 43.7% Spin: |S+,2> 9-th A 3.4454 0.0204 3.4724 28006.99 33 3.4764 eV 0.0000 24.6% Spin: |S+,1> 10-th A 3.4870 -0.0106 3.4830 28092.46 34 3.5252 eV 0.0000 68.4% Spin: |S+,2> 10-th A 3.4870 0.0382 3.5318 28485.50 35 3.6092 eV 0.0000 49.3% Spin: |So,1> 4-th A 3.5132 0.0960 3.6158 29163.42 36 3.6402 eV 0.0000 60.5% Spin: |So,1> 6-th A 3.5920 0.0482 3.6468 29413.12 37 3.6508 eV 0.0000 48.8% Spin: |So,1> 5-th A 3.5648 0.0859 3.6574 29498.52 38 3.6609 eV 0.0000 47.4% Spin: |So,1> 7-th A 3.6206 0.0403 3.6675 29580.42 39 3.6684 eV 0.0000 43.5% Spin: |So,1> 8-th A 3.6288 0.0396 3.6750 29640.60 40 3.7293 eV 0.0000 83.7% Spin: |So,1> 9-th A 3.6898 0.0395 3.7359 30131.95 41 3.7898 eV 0.0000 90.1% Spin: |So,1> 10-th A 3.7487 0.0411 3.7964 30620.26 Print selected matrix elements of [Hsoc] < 0 0 0 |Hso| 2 1 1 > mi/mj ReHso(au) cm^-1 ImHso(au) cm^-1 . 1 1 0.0003219734 70.6650036601 0.0009582030 210.3012602778 1 2 0.0000000000 0.0000000000 -0.0006544171 -143.6279497862 1 3 0.0003219734 70.6650036601 -0.0009582030 -210.3012602778 [tddft_soc_final] |
}}} Then, "imatrso" is specified to define transition dipole moments need to be printed. The number "5" require transition dipoles between 5-pairs of states to be print. The following 5 lines define which pairs will be printed. Here, we require transition dipoles between the first state and five states are printed. === imatnso === === imatnsf === === idiag === By default, idiag=0 uses full diagonalization (preferred for small model space). If idiag=1, then TD-DFT/SOC can use Davidson's algorithm also, along with a specification for the no. of states by '''iexit'''. === iact === =1, allows to use active space specification for the projected active-orbital SOC Hamiltonian (P*HSOC*P), '''eup''' can be specified in (eV) to give a cut off to define active physically interested excited states. == Stability analysis == === isab === === isave === == memory control == === memjkop === == Others == === isgn === === ivo === == Modified Davidson algorithm == === Eneshift === Specify an energy window. States with excitation energies close to input value will be calculate. The energy unit is eV. {{{ $TDDFT Eneshift 9.0 ... $End }}} == AO-TDDFT and AO-TDA == {{{ AO-TDDFT supports R-TDDFT, U-TDDFT, R-TDDFT-SF+1. The possible combinations are imethod=1, itda=0, isf=0 imethod=1, itda=0, isf=1 imethod=2, itda=0, isf=0 AO-TDA supports R-TDA,U-TDA, R-TDA-SF+1, R-TDA-SF-1, U-TDA-SF3. The possible combinations are imethod=1, itda=1, isf=0 imethod=1, itda=1, isf=1 imethod=2, itda=1, isf=0 imethod=2, itda=1, isf=-1 imethod=2, itda=1, isf=3 }}} |
tddft: time-dependent density functional theory
Contents
Time dependent DFT/HF calculation. Support Full TDDFT, TDA and RPA.
Quick guides
The following examples give the minimal inputs for starting TD-DFT calculations.
1. Closed-shell Systems : R-TD-DFT
2. Open-shell Systems : U-TD-DFT and spin-adapted TD-DFT for spin-conserving excitations
3. Open-shell Systems : Spin-flip TD-DFT for spin-flip excitations
5. TD-DFT with SOC: Kramers pairs
6. Excitation analyze based on molecular fragments
General keywords
imethod
imethod 1, R-TDDFT, start from RKS imethod 2, U-TDDFT, start from UKS or ROKS imethod 3, X-TDDFT, start from ROKS
isf
Spin flip TDDFT. isf 0, do not flip isf 1, spin flip up isf -1, spin flip down
itda
itda 0, TDDFT, do not use TDA itda 1, TDA
idrpa
ispa
ialda
thrdab
itest
icorrect
itrans
iro
icv
ioo
iksf
iact
iact = 1: define active space based on energy [elw,eup]
elw
lower bound in eV (not in au!).
eup
upper bound in eV.
idiag
ndiag
aokxc
Convergence threshold
crit_e
crit_vec
States specification
iexit
The number of calculated excited states of each irreducible representation for a specific point group
nexit
Same as above
Save eigenvectors
istore
Integer: specify the file no. to store TDDFT information
lefteig
By default, in TD-DFT the left eigenvector X-Y is also stored.
output eigenvector control
nprt
cthrd
TD-DFT/SOC and Property evaluation
nfiles
No. of TD-DFT calculations to be loaded.
isoc
=1, Only work for closed-shell case (NOT recommended!)
=2, General SOC state interaction
=3, just print SOC matrix elements between two spin-free states (without diagonalization Hsoc).
ifgs
=0, default for not including ground state (GS) in SOC treatment; =1, include GS.
imatsoc
Define SOC matrices need to be calculated. Input format looks like
... #SCF calculation for the ground state S0. It is a singlet. $scf spin 0 ... $end #First TDDFT, singlets S0-S9. $tddft imethod 1 isf 0 iext 10 .... $end #Second TDDFT, triplet T1-T10 $tddft imethod 1 isf 1 iexit 10 $end $tddft .... imatsoc 7 0 0 0 2 1 1 0 0 0 2 1 2 1 1 1 2 1 1 1 1 1 2 1 2 1 1 2 2 1 1 1 1 2 2 1 2 2 1 1 2 1 1 2 1 1 2 1 2 $end
In this input, 7 means seven of SOC matrices will be calculate (If the number <0, then ALL possible HSOC mat will be printed !). Here, it is very tricky to specify states:
- The string "0 0 0" always treat as the ground state.
For other states, three numbers "n m n" represent "ith-tddft", "symmetry" and "ithstate" respectively. Therefore, the first matrix element "0 0 0 2 1 1" means SOC matrix of <S0|HSOC|T1>. The third matrix element "1 1 1 2 1 1" means SOC matrix <S1|HSOC|T1>. Here, the first "1" in bra state "1 1 1" means the state from first TDDFT calculation. The second and third "1" in the bra state "1 1 1" means this state has spatial symmetry "1" and is the first excited state.
imatrsf
Transition dipole between Spin-free states. The input is similar to imatsoc (but currently selected printing is not implemented). Simply use -1 to print all of them.
imatrso
Define transition dipole moment need to be printed between two SOC-included states. Input format looks like(notice we omit other input in TDDFT module)
$TDDFT ... imatrso 5 1 1 1 2 1 3 1 4 1 5 ... $END
Then, "imatrso" is specified to define transition dipole moments need to be printed. The number "5" require transition dipoles between 5-pairs of states to be print. The following 5 lines define which pairs will be printed. Here, we require transition dipoles between the first state and five states are printed.
imatnso
imatnsf
idiag
By default, idiag=0 uses full diagonalization (preferred for small model space).
If idiag=1, then TD-DFT/SOC can use Davidson's algorithm also, along with a specification for the no. of states by iexit.
iact
=1, allows to use active space specification for the projected active-orbital SOC Hamiltonian (P*HSOC*P), eup can be specified in (eV) to give a cut off to define active physically interested excited states.
Stability analysis
isab
isave
memory control
memjkop
Others
isgn
ivo
Modified Davidson algorithm
Eneshift
Specify an energy window. States with excitation energies close to input value will be calculate. The energy unit is eV.
$TDDFT Eneshift 9.0 ... $End
AO-TDDFT and AO-TDA
AO-TDDFT supports R-TDDFT, U-TDDFT, R-TDDFT-SF+1. The possible combinations are
imethod=1, itda=0, isf=0
imethod=1, itda=0, isf=1
imethod=2, itda=0, isf=0
AO-TDA supports R-TDA,U-TDA, R-TDA-SF+1, R-TDA-SF-1, U-TDA-SF3. The possible combinations are
imethod=1, itda=1, isf=0
imethod=1, itda=1, isf=1
imethod=2, itda=1, isf=0
imethod=2, itda=1, isf=-1
imethod=2, itda=1, isf=3