Dimer ASD — BAGEL Manual

# Dimer ASD

## Description

The active space decomposition algorithm for molecular dimers allows for efficient computation of the dimer’s complete-active-space wave functions. The current algorithm works for dimer molecules whose fragments are not covalently linked. Full-CI and restricted-active-space-CI can be used to obtain the fragment state wave functions. ASD calculation starts with dimer molecule construction, see Dimer Construction section for more information.

## Dimer Construction

- Description
- Keywords
- Prerequisite

## Keywords

### Required Keywords

`method`

Description: Method to compute active subspaces.
Datatype: string
Value:
`cas` or `fci`: use full configuration interaction method
`ras`: use restricted active space configuration interaction method

`fci`

Description: If `fci` is used, specify the implementations here.
Recommendation: See Full configuration interaction (FCI) for details.

`ras`

Description: If `ras` is used, specify the implementations here.
Recommendation: See Restricted active space configuration interaction (RASCI) for details.

`space`

Description: Specify important fragment states with the following keys:
`charge`, `spin`, `nstate`
Recommendation: See sample input for details.

### Optional Keywords

`nstates`

Description: Number of target states.
Datatype: int
Default 10

`charge`

Description: Dimer charge.
Datatype: int
Default: 0

`nspin`

Description: Number of dimer total spin.
Datatype: int
Default: 0

`nguess`

Description: Number of initial guess state vectors for Davidson diagonalization.
Datatype: int
Default: \(10\times nstates\)

`Davidson_subspace`

Description: Size of Davidson subspace.
Datatype: int
Default: 10

`max_iter`

Description: Maximum number of iterations for Davidson diagonalization.
Datatype: int
Default: 50

`dipoles`

Description: Whether to calculate dipole moment.
Datatype: bool
Default: false

`thresh`

Description: Threshold for convergence in Davidson diagonalization.
Datatype: double
Default: \(1.0\times 10^{-7}\)

`print_thresh`

Description: Threshold for printing out important configurations.
Datatype: double
Default: 0.01

`store matrix`

Description: Whether the Hamiltonian matrix is stored.
Datatye: bool
Default: false

`print_info`

Description: Whether print out information (e.g. reduced density matrix and energy).
Datatype: bool
Default: false

## Example

Here is a sample calculation of a benzene dimer molecule.

### Sample input

    { "bagel" : [

    {
      "title" : "molecule",
      "basis" : "svp",
      "df_basis" : "svp-jkfit",
      "angstrom" : false,
      "cartesian" : false,
      "geometry" : [
        {"atom" :"C", "xyz" : [    0.00000000000,     0.00000000000,     2.64112304663] },
        {"atom" :"C", "xyz" : [    2.28770766388,     0.00000000000,     1.32067631141] },
        {"atom" :"C", "xyz" : [    2.28770047235,     0.00000000000,    -1.32071294538] },
        {"atom" :"C", "xyz" : [    0.00000000000,     0.00000000000,    -2.64114665444] },
        {"atom" :"C", "xyz" : [   -2.28770047235,     0.00000000000,    -1.32071294538] },
        {"atom" :"C", "xyz" : [   -2.28770766388,     0.00000000000,     1.32067631141] },
        {"atom" :"H", "xyz" : [    4.07221260176,     0.00000000000,     2.35164689765] },
        {"atom" :"H", "xyz" : [    4.07221517814,     0.00000000000,    -2.35163163881] },
        {"atom" :"H", "xyz" : [    0.00000000000,     0.00000000000,    -4.70191324441] },
        {"atom" :"H", "xyz" : [   -4.07221517814,     0.00000000000,    -2.35163163881] },
        {"atom" :"H", "xyz" : [   -4.07221260176,     0.00000000000,     2.35164689765] },
        {"atom" :"H", "xyz" : [    0.00000000000,     0.00000000000,     4.70197960246] }
      ]
    },

    {
      "title" : "hf"
    },

    {
      "title" : "dimerize",
      "angstrom" : true,
      "translate" : [0.0, 4.0, 0.0],
      "dimer_active" : [17, 20, 21, 22, 23, 24],
      "hf" : {
        "thresh" : 1.0e-12
      },
      "localization" : {
        "max_iter" : 50,
        "thresh" : 1.0e-8
      }
    },

    {
      "title" : "asd",
      "method" : "cas",
      "store_matrix" : false,
      "space" : [
        { "charge" : 0, "spin" : 0, "nstate" : 3},
        { "charge" : 0, "spin" : 2, "nstate" : 3},
        { "charge" : 1, "spin" : 1, "nstate" : 3},
        { "charge" :-1, "spin" : 1, "nstate" : 3}
      ],
      "fci" : {
        "thresh" : 1.0e-6,
        "algorithm" : "kh",
        "nguess" : 400
      },
      "nstates" : 5
    }

    ]}

## Reference

Description of Reference | Reference
--- | ---
Active Space Decompotion Method | S. M. Parker, T. Seideman, M. A. Ratner, and T. Shiozaki, J. Chem. Phys. 139, 021108 (2013).