Relativistic complete active space self-consistent field (RelCASSCF)

Description

The relativistic analogue of CASSCF is implemented in BAGEL. The second-order algorithm which is basically the same as its non-relativistic analogue is used by default.

Title: zcasscf

Keywords

state

Description: Number of states computed for each spin value. All are included in the state-averaging procedure when orbitals are optimized.
Datatype: vector<int>
Default: There is no default; this parameter must be supplied in the input.
Note: An array of integers is supplied, where each one indicates the number of states for a given spin value. For example, the input [ 1 ] gives a singlet ground state, while [ 3, 0, 1 ] gives three singlets and one triplet (6 states total). Be careful! While the spin values you specified are used in generating guess CI coefficients, the spin sectors will mix, and the algorithm returns the n lowest eigenstates regardless of their spin expectation values.

nact

Description: Number of active orbitals
Datatype: int
Default: 0

nclosed

Description: Number of closed orbitals
Datatype: int
Default: Number of electrons / 2.

active

Description: Specify active orbitals. Note that the orbital index starts from 1.
Datatype: vector<int>
Default: Nact / 2 orbitals lower and higher from the valence orbital.
Example:
[36, 37, 39] : include 36th, 37th, and 39th orbitals.

charge

Description: Molecular charge.
Datatype: int
Default: 0

algorithm

Description: Orbital optimization algorithm.
Datatype: string
Values:
second: second-order algorithm.
noopt: no orbital optimization.
Default: second

gaunt

Description: Turns on the Gaunt interaction in the Hamiltonian.
Datatype: bool
Default: false

breit

Description: Turns on the full Breit interaction in the Hamiltonian.
Datatype: bool
Default: value copied from “gaunt” (if gaunt is true, breit is true)
Recommendation: Usually the Breit contribution is not important for molecular properties.

only_electrons

Description: This option allows the user to freeze all positronic orbitals and optimize only for rotations between electronic orbitals.
Datatype: bool
Default: false

natocc

Description: If set to “true,” occupation numbers of natural orbitals within the active space will be printed to casscf.log after each macroiteration.
Datatype: bool
Default: false

canonical

Description: If set to “true,” optimized orbitals will be transformed to semi-canonical orbitals.
Datatype: bool
Default: false.

hcore_guess

Description: If set to true, the one-electron Hamiltonian is diagonalized to generate initial guess orbitals.
Datatype: bool
Default: false

maxiter

Description: Maximum number of macroiterations.
Datatype: int
Default: 100

maxiter_micro

Description: Maximum number of microiterations.
Datatype: int
Default: 20

maxiter_fci

Description: Maximum number of iterations in CI coefficient optimization
Datatype: int
Default: copied from maxiter

thresh_fci

Description: Convergence threshold for the CI coefficients
Datatype: double
Default: Value copied from thresh

conv_ignore

Description: If set to “true,” BAGEL will continue running even if the maximum iterations is reached without convergence. Normally an error is thrown and the program terminates.
Datatype: bool
Default: false.

restart_cas

Description: If set to “true”, after each macroiteration the orbitals will be written to a binary archive with filename “zcasscf_<iter>.archive”. They can be read back in using the “load_ref” module.
Datatype: bool
Default: false.

pop

Description: If set to true, population analysis of the molecular orbitals will be printed to a file names dhf.log.
Datatype: bool
Default: false

davidson_subspace

Description: Number of vectors retained in the limited-memory Davidson algorithm.
Datatype: int
Default: 20
Recommendation: Reduce if an insufficient amount of memory is available (do not reduce to a value lower than 3).

print_thresh

Description: Threshold below which CI coefficients are not printed.
Datatype: double
Default: 0.05

spin_adapt

Description: Spin-adapt the starting guess.
Datatype: bool
Default: true
Recommendation: Use false if the error “generate_guess produced an invalid determinant” is generated.

aniso

Description: Performs magnetic anisotropy analysis using a pseudospin Hamiltonian, to obtain g-factors and zero-field splitting parameters
Datatype: input block with several paramaters, given below:


nspin

Description: 2 * the spin value of the pseudospin Hamiltonian
Datatype: integer
Default: Number of states in the CASSCF calculation minus one

ranks

Description: Which ranks of the Extended Stevens Operators to include in the zero-field splitting Hamiltonian
Datatype: Array of integers
Default: Even integers from 2 to nspin
Recommendation: Normally use default. The array [ 2, 4, 6 ] can be used to specify the commonly-used sixth-order Hamiltonian if using the giant spin approximation.

print_operators

Description: Option to print additional information. If true, the Extended Stevens Operators will be printed in matrix form, along with the magnetic moment, spin, and orbital angular momentum matrices.
Datatype: bool
Default: false

zaxis and xaxis

Description: Can be used to specify the orientation of the axes along which we should quantize the spin when mapping the zero-field anisotropy
Datatype: Arrays of 3 doubles
Default: The primary g-anisotropy axes are used

states

Description: Which electronic states are to be mapped to the pseudospin Hamiltonian
Datatype: Array of integers
Default: The lowest-lying states are used

center

Description: Coordinates of the spin center (typically a metal atom for a mononuclear complex), given in Bohr radii
Datatype: Arrays of 3 doubles
Default: [ 0.0, 0.0, 0.0 ]

energies

Description: Energies to be used in the anisotropy analysis. This option can be used to replace the CASSCF energies with those generated using another method, such as CASPT2.
Datatype: Arrays of nspin+1 doubles
Default: The relativistic CASSCF energies are used.
Recommendation: Use the default. This option is deprecated now that the “aniso” module is interfaced directly to relativistic CASPT2 and MRCI.

diagop

Description: Operator to be diagonalized in order to determine a mapping from ab initio electronic states to pseudospin states.
Datatype: string - can be “Mu” for magnetic moment, “J”, “S”, or “L”
Default: Mu

phases and phase_full

Description: This is a debugging tool. It allows the use to apply an arbitrary phase shift to the pseudospin states.
Datatype: Array of doubles; double
Default: No phase shift is applied

Example

{ "bagel" : [

{
  "title" : "molecule",
  "basis" : "svp",
  "df_basis" : "svp-jkfit",
  "angstrom" : false,
  "geometry" : [
    { "atom" : "F",  "xyz" : [ 0.000000, 0.000000, 3.720616 ]},
    { "atom" : "H",  "xyz" : [ 0.000000, 0.000000, 0.305956 ]}
  ]
},

{
  "title"  : "zcasscf",
  "state" : [1],
  "thresh" : 5.0e-7,
  "nact"   : 2,
  "nclosed"  : 4
}

]}

from which one obtains

---------------------------
    CASSCF calculation
---------------------------

*** Geometry (Relativistic) ***
     - 3-index ints post                         0.00
     - 3-index ints prep                         0.00
     - 3-index ints                              0.00
     - 3-index ints post                         0.00

     - Geometry relativistic (total)             0.01

  * nclosed  :      4
  * nact     :      2
  * nvirt    :     32
  * gaunt    : false
  * breit    : false
  * active space: 2 electrons in 2 orbitals
  * time-reversal symmetry will be assumed.
     - Coulomb: half trans                       0.01
     - Coulomb: metric multiply                  0.03
     - Coulomb: J operator                       0.00
     - Coulomb: K operator                       0.00
  * nstate   :      1

=== Dirac CASSCF iteration (svp) ===

 * Using the second-order algorithm

       0   0        -99.87309219     1.03e-02      0.07

       res : 1.24e-01   lamb: 1.00e+00   eps : -4.46e-02   step: 2.31e-01    0.06
       res : 2.29e-02   lamb: 1.00e+00   eps : -4.93e-02   step: 2.94e-01    0.06
       res : 2.90e-03   lamb: 1.00e+00   eps : -4.94e-02   step: 2.93e-01    0.05
       res : 8.08e-04   lamb: 1.00e+00   eps : -4.94e-02   step: 2.94e-01    0.05
       res : 1.96e-04   lamb: 1.00e+00   eps : -4.94e-02   step: 2.94e-01    0.05
       res : 3.17e-04   lamb: 1.00e+00   eps : -4.94e-02   step: 2.94e-01    0.05
       res : 1.13e-04   lamb: 1.00e+00   eps : -4.94e-02   step: 2.94e-01    0.06
       res : 1.91e-05   lamb: 1.00e+00   eps : -4.94e-02   step: 2.94e-01    0.06
       1   0        -99.90008454     9.20e-04      0.57

       res : 7.91e-03   lamb: 1.00e+00   eps : -2.52e-04   step: 1.27e-02    0.06
       res : 1.77e-03   lamb: 1.00e+00   eps : -2.72e-04   step: 1.61e-02    0.05
       res : 5.19e-04   lamb: 1.00e+00   eps : -2.75e-04   step: 1.68e-02    0.05
       res : 7.75e-04   lamb: 1.00e+00   eps : -2.75e-04   step: 1.75e-02    0.05
       res : 5.66e-04   lamb: 1.00e+00   eps : -2.76e-04   step: 1.84e-02    0.06
       res : 2.02e-04   lamb: 1.00e+00   eps : -2.76e-04   step: 1.89e-02    0.05
       res : 6.00e-05   lamb: 1.00e+00   eps : -2.76e-04   step: 1.90e-02    0.06
       res : 6.44e-06   lamb: 1.00e+00   eps : -2.76e-04   step: 1.90e-02    0.06
       res : 1.06e-06   lamb: 1.00e+00   eps : -2.76e-04   step: 1.90e-02    0.06
       2   0        -99.90024315     1.95e-04      0.62

       res : 1.42e-03   lamb: 1.00e+00   eps : -1.03e-05   step: 2.44e-03    0.06
       res : 3.04e-04   lamb: 1.00e+00   eps : -1.11e-05   step: 3.12e-03    0.05
       res : 9.86e-05   lamb: 1.00e+00   eps : -1.11e-05   step: 3.18e-03    0.05
       res : 4.00e-05   lamb: 1.00e+00   eps : -1.11e-05   step: 3.19e-03    0.05
       res : 4.83e-05   lamb: 1.00e+00   eps : -1.11e-05   step: 3.20e-03    0.06
       res : 3.89e-05   lamb: 1.00e+00   eps : -1.12e-05   step: 3.24e-03    0.06
       res : 1.11e-05   lamb: 1.00e+00   eps : -1.12e-05   step: 3.25e-03    0.06
       res : 2.28e-06   lamb: 1.00e+00   eps : -1.12e-05   step: 3.25e-03    0.05
       res : 4.11e-07   lamb: 1.00e+00   eps : -1.12e-05   step: 3.25e-03    0.05
       res : 9.17e-08   lamb: 1.00e+00   eps : -1.12e-05   step: 3.25e-03    0.05
       3   0        -99.90025026     5.44e-05      0.67

       res : 3.82e-04   lamb: 1.00e+00   eps : -7.76e-07   step: 6.56e-04    0.05
       res : 8.18e-05   lamb: 1.00e+00   eps : -8.31e-07   step: 8.43e-04    0.05
       res : 2.63e-05   lamb: 1.00e+00   eps : -8.36e-07   step: 8.59e-04    0.05
       res : 9.66e-06   lamb: 1.00e+00   eps : -8.36e-07   step: 8.61e-04    0.06
       res : 1.02e-05   lamb: 1.00e+00   eps : -8.36e-07   step: 8.61e-04    0.06
       res : 1.06e-05   lamb: 1.00e+00   eps : -8.37e-07   step: 8.71e-04    0.05
       res : 2.98e-06   lamb: 1.00e+00   eps : -8.37e-07   step: 8.73e-04    0.05
       res : 6.25e-07   lamb: 1.00e+00   eps : -8.37e-07   step: 8.73e-04    0.05
       res : 1.21e-07   lamb: 1.00e+00   eps : -8.37e-07   step: 8.73e-04    0.05
       4   0        -99.90025079     1.49e-05      0.60

       res : 1.04e-04   lamb: 1.00e+00   eps : -5.79e-08   step: 1.78e-04    0.05
       res : 2.24e-05   lamb: 1.00e+00   eps : -6.20e-08   step: 2.29e-04    0.05
       res : 7.19e-06   lamb: 1.00e+00   eps : -6.23e-08   step: 2.34e-04    0.05
       res : 2.64e-06   lamb: 1.00e+00   eps : -6.23e-08   step: 2.34e-04    0.06
       res : 2.77e-06   lamb: 1.00e+00   eps : -6.24e-08   step: 2.35e-04    0.05
       res : 2.90e-06   lamb: 1.00e+00   eps : -6.24e-08   step: 2.37e-04    0.05
       res : 8.21e-07   lamb: 1.00e+00   eps : -6.24e-08   step: 2.38e-04    0.05
       res : 1.72e-07   lamb: 1.00e+00   eps : -6.24e-08   step: 2.38e-04    0.05
       5   0        -99.90025083     4.07e-06      0.55

       res : 2.83e-05   lamb: 1.00e+00   eps : -4.30e-09   step: 4.86e-05    0.05
       res : 6.10e-06   lamb: 1.00e+00   eps : -4.61e-09   step: 6.25e-05    0.05
       res : 1.96e-06   lamb: 1.00e+00   eps : -4.63e-09   step: 6.37e-05    0.06
       res : 7.19e-07   lamb: 1.00e+00   eps : -4.64e-09   step: 6.39e-05    0.05
       res : 7.56e-07   lamb: 1.00e+00   eps : -4.64e-09   step: 6.39e-05    0.06
       res : 7.92e-07   lamb: 1.00e+00   eps : -4.64e-09   step: 6.46e-05    0.05
       res : 2.25e-07   lamb: 1.00e+00   eps : -4.64e-09   step: 6.48e-05    0.06
       6   0        -99.90025083     1.11e-06      0.51

       res : 7.70e-06   lamb: 1.00e+00   eps : -3.20e-10   step: 1.32e-05    0.06
       res : 1.66e-06   lamb: 1.00e+00   eps : -3.43e-10   step: 1.70e-05    0.05
       res : 5.35e-07   lamb: 1.00e+00   eps : -3.44e-10   step: 1.74e-05    0.06
       res : 2.00e-07   lamb: 1.00e+00   eps : -3.45e-10   step: 1.74e-05    0.05
       7   0        -99.90025083     3.03e-07      0.36

  * Second-order optimization converged. *

References

BAGEL references

Description of Reference Reference
Relativistic CASSCF J. E. Bates and T. Shiozaki, J. Chem. Phys. 142, 044112 (2015).
Second-order Relativistic CASSCF R. D. Reynolds, T. Yanai, and T. Shiozaki, arXiv:1804.06470 (2018).

General references

Description of Reference Reference
General text on relativistic electronic structure M. Reiher and A. Wolf, Relativistic Quantum Chemistry (Wiley-VCH, Weinheim, 2009).