Which types of SCF are supported with the $multipole_field section? I am particularly interested in ROKS calculations. A simple test:
$comment
Ground state calculation.
$end
$molecule
0 1
O 0.0000000 0.0000000 0.1173000
H 0.0000000 0.7572000 -0.4692000
H 0.0000000 -0.7572000 -0.4692000
$end
$rem
METHOD PBE
BASIS pcseg-1
MEM_TOTAL 8000
MEM_STATIC 100
SCF_CONVERGENCE 8
SYMMETRY FALSE
SYM_IGNORE TRUE
THRESH 14
$end
@@@
$comment
ROKS calculation on water - without field
$end
$molecule
read
$end
$rem
ROKS TRUE
METHOD PBE
BASIS pcseg-1
MEM_TOTAL 8000
MEM_STATIC 100
SCF_CONVERGENCE 8
SCF_GUESS READ
SYMMETRY FALSE
SYM_IGNORE TRUE
THRESH 14
$end
@@@
$comment
ROKS calculation on water - with field
$end
$molecule
read
$end
$rem
ROKS TRUE
METHOD PBE
BASIS pcseg-1
MEM_TOTAL 8000
MEM_STATIC 100
SCF_CONVERGENCE 8
SCF_GUESS READ
SYMMETRY FALSE
SYM_IGNORE TRUE
THRESH 14
$end
$multipole_field
z 0.0001
$end
runs and indeed produces a Stark shift in the excited state energy. I ran a more complex example:
$comment
Ground state calculation on water.
$end
$molecule
0 1
O 0.0000000 0.0000000 0.1173000
H 0.0000000 0.7572000 -0.4692000
H 0.0000000 -0.7572000 -0.4692000
$end
$rem
METHOD SCAN
BASIS GEN
PURECART 11
MEM_TOTAL 8000
MEM_STATIC 100
SCF_CONVERGENCE 8
SYMMETRY FALSE
SYM_IGNORE TRUE
THRESH 14
$end
$basis
H 0
aug-pcseg-2
****
O 0
aug-pcx-2
****
$end
@@@
$comment
ROKS calculation on 1s -> 3s excited state of water - no field
$end
$molecule
read
$end
$rem
DELTA_SCF TRUE
METHOD SCAN
BASIS GEN
PURECART 11
MEM_TOTAL 8000
MEM_STATIC 100
SCF_CONVERGENCE 8
SCF_GUESS READ
SYMMETRY FALSE
SYM_IGNORE TRUE
THRESH 14
$end
$delta_scf
SOMO_1 1
singlet restricted
singlet_SCF_algorithm SGM
singlet_SOMO_print alpha
$end
$plots
grid_spacing 0.35
grid_range 5.0
$end
$basis
H 0
aug-pcseg-2
****
O 0
aug-pcx-2
****
$end
@@@
$comment
ROKS calculation on 1s -> 3s excited state of water - with field (6e-2)
$end
$molecule
read
$end
$rem
DELTA_SCF TRUE
METHOD SCAN
BASIS GEN
PURECART 11
MEM_TOTAL 8000
MEM_STATIC 100
SCF_CONVERGENCE 8
SCF_GUESS READ
SYMMETRY FALSE
SYM_IGNORE TRUE
THRESH 14
$end
$delta_scf
SOMO_1 1
singlet_SCF_algorithm SGM
singlet restricted
$end
$basis
H 0
aug-pcseg-2
****
O 0
aug-pcx-2
****
$end
$multipole_field
z 0.06
$end
@@@
$comment
ROKS calculation on 1s -> 3s excited state of water - with field (-6e-2)
$end
$molecule
read
$end
$rem
DELTA_SCF TRUE
METHOD SCAN
BASIS GEN
PURECART 11
MEM_TOTAL 8000
MEM_STATIC 100
SCF_CONVERGENCE 8
SCF_GUESS READ
SYMMETRY FALSE
SYM_IGNORE TRUE
THRESH 14
$end
$delta_scf
SOMO_1 1
singlet_SCF_algorithm SGM
singlet restricted
$end
$basis
H 0
aug-pcseg-2
****
O 0
aug-pcx-2
****
$end
$multipole_field
z -0.06
$end
and the results seem to agree well with Fig 4. of https://doi.org/10.1021/acs.jpca.2c08311, so I am tempted to conclude that the calculation works. However, wanted to verify with you to be certain, as there is no information in the manual about this.