Relativistic multireference second-order perturbation theory (RelCASPT2) — BAGEL Manual

# Relativistic multireference second-order perturbation theory (RelCASPT2)

## Description

The relativistic version of the fully internally contracted CASPT2. As in its non-relativistic analogue, single-state calculations, multi-state calculations, and its extended variant are available. Of course, this is implemented with the automatic code generator SMITH3.

Title: `relsmith`

## Keywords

### CASSCF keywords

See Relativistic complete active space self-consistent field (RelCASSCF).

### SMITH keywords

The default values are recommended unless mentioned otherwise.

`method`

Description: Do multistate CASPT2.
Datatype: string
Values:
`caspt2`: Standard CASPT2.
`casa` : Use Dyall’s Hamiltonian

`ms`

Description: Do multistate CASPT2.
Datatype: bool
Default: true.

`xms`

Description: Do extended multistate CASPT2.
Datatype: bool
Default: true.

`sssr`

Description: Use SS-SR contraction scheme.
Datatype: bool
Default: true.

`shift`

Description: Vertical shift.
Datatype: double precision
Default: 0.0

`thresh`

Description: Convergence threshold.
Datatype: double precision
Default: For single point energy calculation, 1.0e-6. Tight convergence for gradient calculation, 1.0e-8.

`thresh_overlap`

Description: Overlap cutoff threshold for internally contracted basis.
Datatype: Double precision
Default: 1.0e-9

`frozen`

Description: Freeze core orbitals.
Datatype: bool
Default: true

`ncore`

Description: Number of frozen core orbitals.
Datatype: int
Default: If `frozen` is true, subvalence orbitals are frozen. If false, zero.

`nfrozenvirt`

Description: Number of frozen virtual orbitals.
Datatype: int
Default: 0

`block_diag_fock`

Description: Using a block-diagonal zeroth-order Hamiltonian
Datatype: bool
Default: false.

`maxiter`

Description: Maximum number of iterations in CASPT2 calculations.
Datatype: int
Default: 50

`maxtile`

Description: Maximum number of orbitals in a single data tile used in CASPT2.
Datatype: int
Default: 10

`davidson_subspace`

Description: Number of vectors retained in the limited-memory Davidson algorithm.
Datatype: int
Default: 10
Recommendation: Reduce if an insufficient amount of memory is available (do not reduce to a value lower than 3).

## Example

### Sample input

    { "bagel" : [

    {
      "title" : "molecule",
      "basis" : "svp",
      "df_basis" : "svp-jkfit",
      "angstrom" : true,
      "geometry" : [
        { "atom" : "O",  "xyz" : [ 0.000, 0.000, 1.210 ]},
        { "atom" : "O",  "xyz" : [ 0.000, 0.000, 0.000 ]}
      ]
    },

    {
      "title" : "hf",
      "charge" : "+2"
    },

    {
      "title" : "dhf",
      "charge" : "+2"
    },

    {
      "title"  : "zcasscf",
      "algorithm" : "second",
      "charge" : "0",
      "state" : [0, 0, 1],
      "thresh" : 1.0e-7,
      "nclosed"  : 7,
      "nact"   : 2
    },

    {
      "title" : "relsmith",
      "method" : "caspt2",
      "sssr" : "false",
      "ncore" : 2,
      "ms" : "true",
      "xms" : "true",
      "shift" : "0.0"
    }

    ]}

from which one obtains:

    * Zeroth order energy : state  0       -0.4311850266
    * Zeroth order energy : state  1       -0.4310720127
    * Zeroth order energy : state  2       -0.4310720127

      ---- iteration ----

        0    -0.40810539     0.00207948      1.70
        1    -0.40848834     0.00016074      1.74
        2    -0.40849019     0.00000849      1.71
        3    -0.40849020     0.00000034      1.70

        0    -0.40811484     0.00207947      1.71
        1    -0.40849779     0.00016074      1.68
        2    -0.40849965     0.00000849      1.69
        3    -0.40849965     0.00000034      1.75

        0    -0.40811484     0.00207947      1.73
        1    -0.40849779     0.00016074      1.69
        2    -0.40849965     0.00000849      1.69
        3    -0.40849965     0.00000034      1.71

      -------------------

    * RelCASPT2 energy : state  0     -149.9873960122
    * RelCASPT2 energy : state  1     -149.9873936904
    * RelCASPT2 energy : state  2     -149.9873936904

    * MS-RelCASPT2 Heff
      (-149.9873960122,-0.0000000000)(0.0000000000,0.0000000000)(0.0000000000,-0.0000000000)
      (0.0000000000,-0.0000000000)(-149.9873936904,-0.0000000000)(0.0000000000,0.0000000000)
      (0.0000000000,0.0000000000)(0.0000000000,-0.0000000000)(-149.9873936904,-0.0000000000)

    * MS-RelCASPT2 rotation matrix
      (1.0000000000,0.0000000000)(0.0000000000,0.0000000000)(0.0000000000,0.0000000000)
      (0.0000000000,0.0000000000)(-0.7112091498,0.4043385965)(0.0936202837,-0.5673861886)
      (0.0000000000,0.0000000000)(-0.4948015439,-0.2930243620)(-0.7669166768,0.2848630658)

    * MS-RelCASPT2 energy : state  0     -149.9873960122
    * MS-RelCASPT2 energy : state  1     -149.9873936904
    * MS-RelCASPT2 energy : state  2     -149.9873936904

## References

### BAGEL References

Description of Reference | Reference
--- | ---
SMITH3 | M. K. MacLeod and T. Shiozaki, J. Chem. Phys. 142, 010507 (2015).
Relativistic CASPT2 | T. Shiozaki and W. Mizukami, J. Chem. Theory Comput. 11, 4733 (2015).

### General References

Description of Reference | Reference
--- | ---
CASPT2 | K. Andersson, P.-Å. Malmqvist, and B. O. Roos, J. Chem. Phys. 96, 1218 (1992).
MS-CASPT2 | J. Finley, P.-Å. Malmqvist, B. O. Roos, and L. Serrano-Andres, Chem. Phys. Lett. 288, 299 (1998).
XMCQDPT2 | A. A. Granovsky, J. Chem. Phys. 134, 214113 (2011).
XMS-CASPT2 | T. Shiozaki, W. Győrffy, P. Celani, and H.-J. Werner, J. Chem. Phys. 135, 081106 (2011).