Welcome to Psi4FockCI’s documentation!

This code is a Python package that uses Psi4’s DETCI module to run Fock-space CI (RAS-nSF-IP/EA) calculations. The method handles spin and spatial degeneracies in molecular systems by solving the orbitals of a reference state that can be well-represented by a single determinant, and then using non-particle-conserving and non-spin-conserving operators to obtain the desired state. A more detailed description of the method itself can be found here. Further details about this method, including examples and analysis, can be found in this paper.

Installation

Clone the program from the GitHub repository:

$ git clone https://github.com/shannonhouck/psi4fockci.git

Then navigate into the directory and use pip to install:

$ cd psi4fockci
$ pip install -e .

You can import this as a Python package and use it however you want! If you have pytest installed, you can use it to test your installation:

$ cd psi4fockci
$ pytest

Running CAS-nSF-IP/EA

The plugin can be run directly through Psi4’s energy() call, as with any Psi4 plugin. The number of spin-flips and IP/EA to perform are determined automatically based on the given charge and multiplicity of the target state. In order to run a CAS-1SF-IP/STO-3G calculation, for example, one could set an input file up in the following way:

molecule {
0 7
N 0.0 0.0 0.0
N 0.0 0.0 1.3
symmetry c1
}

set {
  basis cc-pVDZ
}

energy('psi4fockci', new_charge=1, new_multiplicity=1)

The input file can then be fun from the command line:

$ psi4 example.dat

The program can also be run through the run_psi4fockci function call. See the documentation of that function for information about the various options and keywords.

Passing Keywords to Psi4

If running with Psi4, keywords for various modules can be set as normal in the input file:

set detci {
  ci_maxiter 500
  num_roots 7
}

Alternately, keywords can be passed to Psi4 using the add_opts keyword. These options should be put in the dictionary form usually taken by Psi4. For example, if I wanted to change the number of CI roots, I could specify it as follows:

options = {"basis": "sto-3g", "num_roots": 10}
e = psi4.energy('psi4fockci', n2, new_charge=0, new_multiplicity=5, add_opts=options)

Adding Excitations

Excitations are important, particularly for the nSF-IP/EA schemes. (Hole excitations are recommended for IP-type and particle excitations are recommended for EA-type; see the paper for details.) Excitations outside of the CAS space can be requested by setting the conf_space keyword appropriately. The following keywords are valid:

  • "" CAS-nSF-IP/EA (default, no additional excitations)

  • "h" RAS(h)-nSF-IP/EA (hole excitations)

  • "p" RAS(p)-nSF-IP/EA (particle excitations)

  • "S" RAS(S)-nSF-IP/EA (singles)

  • "SD" RAS(SD)-nSF-IP/EA (singles and doubles)

  • "SDT" RAS(SDT)-nSF-IP/EA (singles, doubles, and triples)

A program for running RAS-SF-IP/EA using Psi4.

This program runs RAS-nSF-IP/EA using Psi4’s DETCI module.

Indices and tables