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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。		 ##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. [[TD-DFT with spin-flip calculations]]

4. [[Open-shell Systems : Spin-flip TD-DFT for spin-flip excitations]]

5. [[TD-DFT with SOC]]

6. [[TD-DFT with SOC: open-shell systems]]

7. [[TD-DFT with SOC: Kramers pairs]]

8. [[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
}}}

=== ialda ===

The recommended value for ialda is 2 (ALDA0) for spin-flip TDDFT.

=== itest,icorrect ===

itest=1;icorrect=1 must be setted for X-TD-DFT using the U-TD-DFT subroutines.

=== itrans ===

itrans=1: transform the final eigenvector in U-TD-DFT from the spin-orbital based representation
to spin-adapted basis, e.g., CV(0) and CV(1). This only makes sense when ROKS reference is used.

=== iact,elw,eup ===
iact = 1: define active space based on energy [elw,eup]

elw: lower bound in eV (not in au!).

eup: upper bound in eV.

=== idiag ===
idiag=1: iterative, =2 full diag, =3 iVI diag (TDA and AO-TDDFT supported

=== 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 (nreps)
}}}
== 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.

=== ntoanalyze ===
Natural transition orbital analyze.
{{{
ntoanalyze
  2 # number of states
  1 3 # list of states in NTO analyze.
}}}

== 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
}}}

== Frozen orbital ==
=== Frzorb ===
Only valid for C1 symmetry.
{{{
Frzorb
  4 # number of orbital to be frozen
 1 4 6 7 # orbital list
}}}
=== Frzcore ===
{{{
Frzcore
 1 2 2 1 # number of core orbitals will be frozen in each irrep
}}}
=== Frzvirt ===
{{{
Frzvirt
 2 2 2 2 # number of virtual orbitals will be frozen in each irrep
}}}

== Spin-flip Kernel ==
=== kernelctrl ===
=0; (va-vb)*(rhoa-rhob)/( (rhoa-rhob)^2+thrdab)

=2; old version using 2nd order derivatives
Only affect GGA spin-flip TDDFT with ALDA0

=== thrdab ===
threshold for |rhoa-rhob|

== Some uncommon keywords just for testing methods ==
=== idrpa ===
=== ispa ===
=== iro ===
=== icv ===
=== ioo ===
=== iksf ===

tddft: time-dependent density functional theory

Contents

  1. tddft: time-dependent density functional theory
    1. Quick guides
    2. General keywords
      1. imethod
      2. isf
      3. itda
      4. ialda
      5. itest,icorrect
      6. itrans
      7. iact,elw,eup
      8. idiag
      9. ndiag
      10. aokxc
    3. Convergence threshold
      1. crit_e
      2. crit_vec
    4. States specification
      1. iexit
      2. nexit
    5. Save eigenvectors
      1. istore
      2. lefteig
    6. output eigenvector control
      1. nprt
      2. cthrd
    7. TD-DFT/SOC and Property evaluation
      1. nfiles
      2. isoc
      3. ifgs
      4. imatsoc
      5. imatrsf
      6. imatrso
      7. imatnso
      8. imatnsf
      9. idiag
      10. iact
      11. ntoanalyze
    8. Stability analysis
      1. isab
      2. isave
    9. memory control
      1. memjkop
    10. Others
      1. isgn
      2. ivo
    11. Modified Davidson algorithm
      1. Eneshift
    12. AO-TDDFT and AO-TDA
    13. Frozen orbital
      1. Frzorb
      2. Frzcore
      3. Frzvirt
    14. Spin-flip Kernel
      1. kernelctrl
      2. thrdab
    15. Some uncommon keywords just for testing methods
      1. idrpa
      2. ispa
      3. iro
      4. icv
      5. ioo
      6. iksf

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. TD-DFT with spin-flip calculations

4. Open-shell Systems : Spin-flip TD-DFT for spin-flip excitations

5. TD-DFT with SOC

6. TD-DFT with SOC: open-shell systems

7. TD-DFT with SOC: Kramers pairs

8. 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

ialda

The recommended value for ialda is 2 (ALDA0) for spin-flip TDDFT.

itest,icorrect

itest=1;icorrect=1 must be setted for X-TD-DFT using the U-TD-DFT subroutines.

itrans

itrans=1: transform the final eigenvector in U-TD-DFT from the spin-orbital based representation to spin-adapted basis, e.g., CV(0) and CV(1). This only makes sense when ROKS reference is used.

iact,elw,eup

iact = 1: define active space based on energy [elw,eup]

elw: lower bound in eV (not in au!).

eup: upper bound in eV.

idiag

idiag=1: iterative, =2 full diag, =3 iVI diag (TDA and AO-TDDFT supported

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 (nreps)

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.

ntoanalyze

Natural transition orbital analyze. 

ntoanalyze
  2      # number of states
  1 3   # list of states in NTO analyze.

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

Frozen orbital

Frzorb

Only valid for C1 symmetry. 

Frzorb
  4           # number of orbital to be frozen
 1 4 6 7   # orbital list

Frzcore

Frzcore
 1 2 2 1   # number of core orbitals will be frozen in each irrep

Frzvirt

Frzvirt
 2 2 2 2   # number of virtual orbitals will be frozen in each irrep

Spin-flip Kernel

kernelctrl

=0; (va-vb)*(rhoa-rhob)/( (rhoa-rhob)^2+thrdab)

=2; old version using 2nd order derivatives Only affect GGA spin-flip TDDFT with ALDA0

thrdab

threshold for |rhoa-rhob|

Some uncommon keywords just for testing methods

idrpa

ispa

iro

icv

ioo

iksf

tddft (last edited 2022-10-28 13:20:58 by bsuo)