![/!\](/moin_static197/moniker/img/alert.png "/!\"){kind=small}
You should trust both wikis because the password could be read by the particular administrators.
Response properties based on linear and quadratic response functions
All the following tests can be found in bdf-pkg/tests/input/resp2014/2_rsp
Properties from Linear Response Functions (LRF)
Ground-state polarizabilities: 1_polar_h2o/polar_h2o.inp
Frequency-dependent polarizability of H2O - <<z;z>>(wB) at various frequencies. This covers a lot of nonlinear spectroscopies.
$COMPASS TITLE h2o BASIS sto-3g GEOMETRY O 0.00000000 -0.22490589 0.00000000 H 1.45234993 0.89962357 0.00000000 H -1.45234993 0.89962357 0.00000000 end geometry units bohr $END $XUANYUAN $END $SCF RHF charge 0 spin 1 THRESHCONV 1.d-10 1.d-8 guess hcore $end $resp LINE POLA AOPER DIP-Z BOPER DIP-Z BFREQ 3 0.0 1.0 2.0 #reduced $end
2nd SOC correction to ground-state energy: 1_polar_h2o/soc_hf.inp
<<Hso;Hso>>(wB=0) represents 2nd SOC SOC correction to ground-state energy. The specific form of SOC operator can be chosen in the xuanyuan part. Here, we use the sf-X2C/SOMF(1c) operator combined with the ANO-RCC-VTZP basis:
$COMPASS TITLE h2o BASIS ano-rcc-vtzp GEOMETRY F 0. 0. 0. H 0. 0. 1.732549 end geometry $END $XUANYUAN scalar heff 3 soint hsoc 2 $END $SCF RHF charge 0 #-2 spin 1 THRESHCONV 1.d-10 1.d-8 guess hcore $end $resp LINE POLA AOPER HSO-Y BOPER HSO-Y BFREQ 1 0.0 #reduced $end
Transition moment between ground state and excited state: <0|A|ex>
This part has already been contained in the TD-DFT module for the transition dipole moment between the ground and excited states. Maybe in future there will be a subroutine for other kind of properties.
Properties from Quadratic Response Functions (QRF)
Ground-state hyperpolarizabilities: 2_hyper_h2o/hyper_h2o.inp
Hyperpolarizability <<z;x,x>>(wB,wC) of H2O:
$COMPASS Title h2o Basis sto-3g Geometry O .0000000000 -.2249058930 .0000000000 H 1.4523499293 .8996235720 .0000000000 H -1.4523499293 .8996235720 .0000000000 End geometry units bohr $END $xuanyuan $end $scf RKS DFT BHHLYP charge 0 #-2 spin 1 THRESHCONV 1.d-14 1.d-12 guess hcore $end $resp iprt 0 QUAD HYPE AOPER DIP-Z BOPER DIP-X COPER DIP-X # ffield #EFG-ZZ BFREQ 1 0.3 #0.1 #2.0 CFREQ 1 1.0 #0.1 #2.0 # This gives SHG #reduced $end
2nd SOC correction to dipoles: 2_hyper_h2o/soc_dip.inp
The QRF can be used to compute the 2nd SOC correction to dipoles of closed-shell systems: <<z;Hso,Hso>>(wB=0,wC=0). Here, we simply use the Breit-Pauli form (heff=0) of bare nuclear spin-orbit operator (hsoc=0):
$COMPASS Title h2o Basis sto-3g Geometry O .0000000000 -.2249058930 .0000000000 H 1.4523499293 .8996235720 .0000000000 H -1.4523499293 .8996235720 .0000000000 End geometry units bohr $END $xuanyuan scalar heff 0 soint hsoc 0 $end $scf RHF charge 0 #-2 spin 1 THRESHCONV 1.d-14 1.d-12 guess hcore $end $resp iprt 0 QUAD HYPE AOPER DIP-Z BOPER HSO-Z COPER HSO-Z BFREQ 1 0.0 CFREQ 1 0.0 $end
Two-photo absorption from single residues of QRF: 3_single_h2o/single_h2o.inp
$COMPASS Title nh3 Basis sto-3g Geometry O .0000000000 -.2249058930 .0000000000 H 1.4523499293 .8996235720 .0000000000 H -1.4523499293 .8996235720 .0000000000 End geometry units bohr $END $xuanyuan $end $scf RHF charge 0 #-2 spin 1 THRESHCONV 1.d-14 1.d-12 guess hcore $end $TRAINT tddft orbi hforb $END $tddft imethod 1 nexit 1 0 0 0 itda 0 idiag 1 istore 1 iprt 3 lefteig crit_vec 1.d-8 crit_e 1.d-12 $end $resp iprt 0 QUAD single nfiles 1 method 2 AOPER DIP-Z BOPER DIP-Z BFREQ 1 -0.1 $end
<S|r|S'> from double residues of QRF: 4_double_h2o_dpl/double_h2o.inp
$COMPASS Title h2o Basis sto-3g Geometry O .0000000000 -.2249058930 .0000000000 H 1.4523499293 .8996235720 .0000000000 H -1.4523499293 .8996235720 .0000000000 End geometry units bohr $END $xuanyuan $end $scf RHF charge 0 spin 1 THRESHCONV 1.d-12 1.d-12 guess hcore $end $TRAINT tddft orbi hforb $END $tddft imethod 1 nexit 2 0 0 0 itda 0 idiag 1 istore 1 iprt 3 lefteig crit_vec 1.d-12 $end $resp QUAD double nfiles 1 method 2 AOPER DIP-Z $end
For the diagonal part is exactly the same as that obtained from the derivative of excitation energies:
$resp GEOM norder 0 nfiles 1 method 2 $end
Phosphorescence from single residues of QRF: 5_phos_h2o/phos_h2o.inp
This gives the perturbation correction to the transition dipole moment <S|r|T>, which is zero in the nonrelativistic case.
$COMPASS Title h2o Basis sto-3g Geometry O .0000000000 -.2249058930 .0000000000 H 1.4523499293 .8996235720 .0000000000 H -1.4523499293 .8996235720 .0000000000 End geometry units bohr $END $xuanyuan scalar heff 0 soint hsoc 2 $end $scf RKS DFT BHHLYP charge 0 #-2 spin 1 THRESHCONV 1.d-14 1.d-12 guess hcore $end $TRAINT tddft orbi hforb $END $tddft imethod 1 isf 1 nexit 0 1 0 0 itda 0 idiag 1 istore 1 iprt 3 lefteig crit_vec 1.d-8 crit_e 1.d-12 $end $resp iprt 0 QUAD single nfiles 1 method 2 BFREQ 1 0.0 AOPER DIP-Z BOPER HSO-Z $end
<T|r|T'> from single residues of QRF: 6_t_h2o_dpl
This is similar to the evaluation of <S|r|S'> except now two triplets are calculated in TD-DFT by controlling isf=1.
<S|Hso|T> from double residues of QRF: 7_t_h2o_hso/st_h2o_hsoc.inp
<S|Hso^z|Tz> (st_h2o_hsoc.inp):
$tddft imethod 1 isf 0 nexit 0 0 1 0 itda 0 idiag 1 istore 1 iprt 3 lefteig crit_vec 1.d-8 crit_e 1.d-12 $end $tddft imethod 1 isf 1 nexit 0 0 0 1 itda 0 idiag 1 istore 2 iprt 3 lefteig crit_vec 1.d-8 crit_e 1.d-12 $end $resp QUAD double nfiles 2 method 2 aoper hso-z $end
<T|Hso|T'> from double residues of QRF: 7_t_h2o_hso/tt_h2o_hsoc.inp
<Tz|Hso^z|T'z> (tt_h2o_hsoc.inp):
$tddft imethod 1 isf 1 nexit 0 0 1 1 itda 0 idiag 1 istore 1 iprt 3 lefteig crit_vec 1.d-8 crit_e 1.d-12 $end $resp QUAD double isoc 1 nfiles 1 method 2 AOPER hso-z $end
You will get Spin ranks of B and C do not match that of A ! This is because in the collinear formulation only <Tz|Hso^z|T'z> is possible, which is zero since by means of the Wigner-Eckart theorem, the CG coefficient before it will be <1010|10> which is zero. For <Tx|HSOz|Ty>, which is nonzero, it requires a noncollinear formulation ! (For closed-shell systems, it seems to be ok due to the commutation relation)