OpenMolcas Sample Input Files   2018 November 9

Sijia S. Dong, Andrew M. Sand, Prachi Sharma, Jie J. Bao, Donald G. Truhlar, and Laura Gagliardi

Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, MN 55455, USA

1. General input for single-point MC-PDFT calculations

MC-PDFT calculation of the N2 molecule using tPBE, ftPBE, and tOPBE:
   
&SEWARD 
 coord 
 2 
 Angstrom 
N 0.00 0.00 -0.55 
N 0.00 0.00   0.55 
basis=cc-pvdz 
SYMMETRY
XY YZ XYZ
NODEleted
grid input
grid=ultrafine
end of grid input
End of input

&SCF 

&RASSCF
LINEAR
NACT = 10 0 0 
INACTIVE = 2 0 0 0 2 0 0 0 
RAS2 = 1 1 1 0 1 1 1 0 

>>foreach DFT in (TPBE, FTPBE, TOPBE)
&MCPDFT &END
KSDFT=$DFT
End of input
>>enddo


2. Scaling exchange and correlation terms in MC-PDFT and KS-DFT

2.1 Geometry optimization of the N2 molecule using SS-CAS-PDFT with an HLE-type functional constructed from scaling the exchange term and the correlation term of tPBE by 1.25 and 0.5, respectively.

&SEWARD
coord
2
Angstrom
N 0.0 0.0   0.60
N 0.0 0.0  -0.60
basis
N.ano-rcc-VDZP
group
 full
NODEleted
grid input
grid=ultrafine
end of grid input
NoCD
End of input

&RASSCF &END
LINEAR
nActEl
 5 0 0
FROZen
0 0 0 0 0 0 0 0
INACTIVE
2 0 0 0 2 0 0 0
RAS2
3 3 3 0 1 1 1 0
DELEted
0 0 0 0 0 0 0 0
Symmetry
1
Spin
2

&MCPDFT
 KSDFT=TPBE
 DFCF=1.25 0.5
 GRADIENT

&SLAPAF

2.2 Kohn-Sham density functional theory calculation of the N2 molecule using the B3LYP functional with the correlation terms scaled by a factor of 0.8.

&SEWARD
coord
2
Angstrom
N 0.0 0.0   0.60
N 0.0 0.0  -0.60
basis
N.ano-rcc-VDZP
End of input

&SCF
KSDFT=B3LYP
DFCF=1.0 0.8


3. SS-CAS-PDFT gradient

Geometry optimization of the N2 molecule using SS-CAS-PDFT with the tPBE on-top functional:

&SEWARD
coord
2
Angstrom
N 0.0 0.0   0.60
N 0.0 0.0  -0.60
basis
N.ano-rcc-VDZP
group
 full
NODEleted
grid input
grid=ultrafine
end of grid input
NoCD
End of input

&RASSCF &END
LINEAR
nActEl
 5 0 0
FROZen
0 0 0 0 0 0 0 0
INACTIVE
2 0 0 0 2 0 0 0
RAS2
3 3 3 0 1 1 1 0
DELEted
0 0 0 0 0 0 0 0
Symmetry
1
Spin
2

&MCPDFT
KSDFT=TPBE
GRADIENT

&SLAPAF


4. SI-PDFT

The following is an example SI-PDFT run for the dissociation of LiF:

>>export XX=2.9
>>foreach L in ( 1 .. 30 )
>> eval XX=$XX + 0.1
 &SEWARD
   coord
     2
   angstrom
   F        0.000      0.000    $XX
   Li        0.000     0.000    0.00
   group=full
   basis set = Li.cc-pvdz,F.aug-cc-pvdz
   grid input
   grid
   ultrafine
   end of grid input

 &SCF

 >> COPY $WorkDir/$Project.ScfOrb $CurrDir/INPORB
 >> COPY $WorkDir/$Project.ScfOrb $WorkDir/INPORB

*This is the first RASSCF run.  This is the multistate calculation.
*The JOBIPH generated by this run must be copied to JobIph01.

 &RASSCF &END
   LINEAR
   LUMORB
   NACTEL
     6 0 0
   INACTIVE
     3 0 0 0
   RAS2
     4 2 0 2
   Symmetry
     1
   Spin
     1
   orblisting
   all
   PRWF=0.000001
   CIROOT
   2 2 1

 >> COPY $WorkDir/$Project.JobIph $WorkDir/$Project.JobIph01
 >> RM $WorkDir/$Project.JobIph

*This is the second RASSCF run.  This is the single state used as the reference
*in performing the GS-like orthogonalization.  The JOBIPH generated by this run must
*be copied to JobIph02.

 &RASSCF &END
   LINEAR
   NACTEL
     6 0 0
   INACTIVE
     3 0 0 0
   RAS2
     4 2 0 2
   Symmetry
     1
   Spin
     1
   orblisting
   all
   PRWF=0.000001

 >> COPY $WorkDir/$Project.JobIph $WorkDir/$Project.JobIph02
 >> RM $WorkDir/$Project.JobIph

*This is the first RASSI call.  It generates the new SI states and 
*creates a JOBIPH file called JOBGS.  This first RASSI run requires the
*GSORthog keyword.

  &RASSI
  NROF = 2 2 1
  1 2
  1
  IPHN = JobIph01; JobIph02
  GSORthog

*The JOBGS must be copied to JobIph prior to the MC-PDFT calculation, 
*as that is where the information for the MC-PDFT calculation is taken
*from.

>> COPY $WorkDir/JOBGS $WorkDir/$Project.JobIph

*The MC-PDFT calculation requires a few special keywords:
*GSOR toggles the generation of new density matrices
*NOGRadient is to turn off the calculation of potentials (not needed).
*Since this calculation loops over geometries, MC-PDFT thinks this might be
*a gradient calculation and will calculate potentials, unless explicitly
*prevented through the use of NOGRadient.

  &MCPDFT
  KSDFT=tPBE
  GSOR
  NOGRadient


 >> RM $WorkDir/$Project.JobIph01
 >> RM $WorkDir/$Project.JobIph02
 >> RM $WorkDir/$Project.JobIph

*The JOBGS (which was modified in the MCPDFT part) must be copied
*to JobIph01

 >> COPY $WorkDir/JOBGS $WorkDir/$Project.JobIph01

*The SECOnd keyword must be used in the second call to RASSI

 &RASSI
 NROF = 1 2
 1 2
 IPHN = JobIph01
 SECOnd

 >> RM $WorkDir/JOBGS
>> enddo


5. General input for a single-point DMRG-PDFT calculation 

&GATEWAY 
 coord 
 2 
 Angstrom 
N 0.00 0.00 -0.55 
N 0.00 0.00   0.55 
basis=cc-pvdz 
grid input
grid=ultrafine
end of grid input
End of input
      
&SEWARD 
&SCF 
&RASSCF 
DMRG 
RGINPUT 
nsweeps = 4 
max_bond_dimension = 100 
EndRG 
inactive = 2 0 0 0 2 0 0 0 
RAS2 = 1 1 1 0 1 1 1 0 
LINEAR

&MCPDFT
KSDFT=TPBE


6. Printing orbital second moment <r^2> for all orbitals to identify Rydberg orbitals

We take a trans-1,3-butadiene molecule as an example. First, generate at least one orbital file, such as the CASSCF natural orbitals ($Project.RasOrb, $Project.RasOrb.1, $Project.RasOrb.2, É):

&GATEWAY
Symmetry
XY XYZ
Basis Set
C.aug-cc-pVTZ....
   C1    1.740343 0.616556 0.0000000 /Angstrom
   C2    0.397343 0.616556 0.0000000 /Angstrom
End of Basis
Basis Set
H.cc-pVTZ....
   H3    -0.126346 1.577069 0.000000 /Angstrom
   H4     2.279054 1.568725 0.000000 /Angstrom
   H5    2.279054 -0.335614 0.000000 /Angstrom
End of Basis

&SEWARD
NODEleted
grid input
grid=ultrafine
end of grid input
End of input

&SCF

&RASSCF &END
CIROOT= 3 3 1
nActEl
4 0 0
INACtive
7 0 0 6
FROZen
0 0 0 0
RAS2
0 4 4 0
DELEted
0 0 0 0
Symmetry
4
Spin
1
CHARge
0

Then, to print the orbital <r2> for individual natural orbitals of each of the first two states, $Project.RasOrb.1 and $Project.RasOrb.2, specify 

export MOLCAS_PRINT=3

and use the following input:

&GATEWAY
Symmetry
XY XYZ
Basis Set
C.aug-cc-pVTZ....
   C1    1.740343 0.616556 0.0000000 /Angstrom
   C2    0.397343 0.616556 0.0000000 /Angstrom
End of Basis
Basis Set
H.cc-pVTZ....
   H3    -0.126346 1.577069 0.000000 /Angstrom
   H4     2.279054 1.568725 0.000000 /Angstrom
   H5    2.279054 -0.335614 0.000000 /Angstrom
End of Basis

>>COPY $CurrDir/$Project.RasOrb.1 INPORB

&SEWARD
NODEleted
grid input
grid=ultrafine
end of grid input
VECTors
ORBCon
ORBAll
End of input

>>COPY $CurrDir/$Project.RasOrb.2 INPORB

&SEWARD
NODEleted
grid input
grid=ultrafine
end of grid input
VECTors
ORBCon
ORBAll
End of input

Then, the magnitude of orbital <r^2> and its components (especially its <z^2> component because the molecule is on the xy plane) printed in the output indicates how diffuse an orbital is.