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| === isave === == memory control === |
=== isave === == memory control == |
tddft
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.
Closed-shell Systems : R-TD-DFT
This gives a R-TD-DFT (imethod=1,itda=0) for singlet-singlet (isf=0) transitions using Davidson iterative diagonalization (idiag=1). In each irreducible representations, the lowest 10 states are calculated.
$TDDFT IMETHOD 1 ISF 0 ITDA 0 IDIAG 1 iexit 10 $END
The algorithm used in TD-DFT is the same as in the ground state calculations. If direct SCF is used.
$xuanyuan directhf $end ...
then TD-DFT also uses direct algorithm. The memory for JK operators can be changed by using MemJKOP.
$TDDFT ... MemJKOP 2048 ... $END
If the ERI is stored, then integral transformation should be carried out before TDDFT
$TRAINT TDDFT (or UTDDFT for RO/U case) ORBI hforb $END
Open-shell Systems : U-TD-DFT and spin-adapted TD-DFT for spin-conserving excitations
Using a UKS reference in SCF, the input for U-TD-DFT reads:
$TDDFT IMETHOD 2 ISF 0 ... $END
Using a ROKS reference in SCF, the input for Spin-adapted TD-DFT (X-TD-DFT) can be set in two ways.
One uses U-TD-DFT solver to solve the X-TD-DFT in spin-orbit basis:
$TDDFT IMETHOD 2 ISF 0 ... icorrect 1 itest 1 itrans 1 $END
The option itrans will transform the eigenvector in CV(aa),CV(bb) basis into CV(0) and CV(1) basis.
The other one uses the original spin-adapted TD-DFT solver to solve the X-TD-DFT in spin-tensor basis:
$TDDFT imethod 3 isf 0 ... itest 1 icorrect 1 $END
These two ways give exactly the same excitation energies. The only different is the representation if "itrans" is not used.
Open-shell Systems : Spin-flip TD-DFT for spin-flip excitations
Although SF-TD-DFT is possible by using isf=3, which calculate a->b and b->a excitation at the same time, however, the TDA version is preferred. This allows separate calculations of a->b and b->a types of excitations.
Using a UKS/ROKS reference in SCF, the input for spin-flip TDA (flip-up) reads:
$TDDFT IMETHOD 2 ISF 1 ... ialda 2 $END
The keyword ialda controls the spin-flip kernel when using GGA functionals in ground state calculations. The option "ialda=2" means a ALDA0 type approximation is used, which always gives numerical stable results.
Flip-down excitations can be calculated by choosing isf=-1.
$TDDFT IMETHOD 2 ISF -1 ... ialda 2 $END
There are spin-adapted versions of flip-down excitations with imethod=3, but they are not thoroughly tested and to be explored in future.
General keywords
imethod
isf
itda
idrpa
ispa
ialda
thrdab
itest
icorrect
itrans
iro
icv
ioo
iksf
iact
elw
eup
idiag
ndiag
aokxc
States specification
iext
next
output eigenvector control
nprt
cthrd
Property evaluation
istore
isoc
irsf
irso
insf
inso
imatsoc
imatrsf
imatrso
imatnsf
ifgs
nfiles
isgn
ivo
Stable analyze
isab
isave
memory control
memjkop
TD-DFT/SOC
SOC计算的输入文件中以$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'
...
...
其中，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 $END $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
SOC-SI results:
*** 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]