Single points calculation

The single_points workflow performs single point calculations and can be used, for example, to compute the eigenvalues and energies of triplet orbitals on a singlet geometry or viceversa.

Preparing the input

Basic Example

We start with the very basic example of an input file to perform a single point calculation on the relaxed geometry of a Cd33Se33 system.

workflow:
  single_points

project_name: Cd33Se33
active_space: [50, 50]
compute_orbitals: True
path_hdf5: "Cd33Se33.hdf5"
path_traj_xyz: "Cd33Se33.xyz"
scratch_path: "/tmp/singlepoints_basic"

cp2k_general_settings:
  basis:  "DZVP-MOLOPT-SR-GTH"
  potential: "GTH-PBE"
  cell_parameters: 28.0
  periodic: none
  executable: cp2k.popt

  cp2k_settings_main:
    specific:
      template: pbe_main

  cp2k_settings_guess:
    specific:
      template:
        pbe_guess

In your working directory, create an input_test_single_points_basic.yml file and copy the previous input inside it, by respecting the indentation. Also copy locally the file containing the coordinates of the Cd33Se33 system in an xyz format, Cd33Se33.xyz.

Your input_test_single_points_basic.yml now contains all settings to perform the calculations and needs to be edited according to your system and preferences. Pay attention to the following parameters that are common to all input files: workflow, project_name, active_space, path_hdf5, path_traj_xyz, scratch_path.

workflow: The workflow you need for your calculations, in this case single_points for a single point calculation.
project_name: Project name for the calculations. You can choose what you wish.
active_space: Range of (occupied, virtual) molecular orbitals to be computed. For example, if 50 occupied and 100 virtual should be considered in your calculations, the active space should be set to [50, 100].
compute_orbitals: Specify if the energy and eigenvalues of the selected orbitals are to be computed. The default is set to True.
path_hdf5: Path where the hdf5 should be created / can be found. The hdf5 is the format used to store the molecular orbitals and other information.
path_traj_xyz: Path to the pre-optimized geometry of your system. It should be provided in xyz format.
scratch_path: A scratch path is required to perform the calculations. For large systems, the .hdf5 files can become quite large (hundredths of GBs) and calculations are instead performed in the scratch workspace. The final results will also be stored here.

You can find the complete list of all the general options (common to all workflows) in this dictionary.

In the cp2k_general_settings, you can customize the settings used to generate the cp2k input (see available options in schema_cp2k_general_settings).

Here you can specify the level of theory you want to use in your cp2k calculation (basis set and potential) as well as the main characteristics of your system (cell parameters and angles, periodicity, charge, multiplicity, …).

Note that the (fast) SCF routine in cp2k is based on the Orbital Transformation (OT) method, which works on the occupied orbital subspace. To obtain the full spectrum of molecular orbitals, one should perform a full diagonalization of the Fock matrix. For this reason, to obtain and store both occupied and unoccupied orbitals, defined using the active_space keyword, we have to follow a 2-step procedure: in the first step, which in the yaml input we define as cp2k_settings_guess, we perform a single point calculation using the fast OT approach; then in the second step, defined as cp2k_settings_main, we use the converged orbitals in the first step to start a full diagonalization calculation using the DIIS procedure.

In the cp2k_settings_guess and cp2k_settings_main subsections you can provide more detailed information about the cp2k input settings to be used to compute the guess wavefunction and to perform the main calculation respectively. In this example, we have used one of the available templates, specifically customized for calculations with a PBE exchange-correlation functional. You can use the cp2k manual to further personalize your input requirements.

Advanced Example

We are now ready to move to a more advanced example in which we want to compute the orbitals’ energies and eigenvalues for each point of a pre-computed MD trajectory for our Cd33Se33 system. The input file will look like that:

workflow:
  single_points

project_name: Cd33Se33
active_space: [50, 50]
dt: 1
path_hdf5: "Cd33Se33.hdf5"
path_traj_xyz: "Cd33Se33_fivePoints.xyz"
scratch_path: "/tmp/singlepoints_advanced"
calculate_guesses: "first"

cp2k_general_settings:
  basis:  "DZVP-MOLOPT-SR-GTH"
  potential: "GTH-PBE"
  cell_parameters: 28.0
  periodic: none
  executable: cp2k.popt

  cp2k_settings_main:
    specific:
      template: pbe_main
      cp2k:
        force_eval:
          dft:
            scf:
              eps_scf: 1e-6

  cp2k_settings_guess:
    specific:
      template:
        pbe_guess

In your working directory, create an input_test_single_points_advanced.yml file and copy the previous input inside it (remember to respect the indentation). Also copy locally the small pre-computed MD trajectory of the Cd33Se33 system, Cd33Se33_fivePoints.xyz.

In the input file, pay particular attention to the following parameters that have been added/modified with respect to the previous example:

dt: The size of the timestep used in your MD simulations (in fs).
path_traj_xyz: Path to the pre-computed MD trajectory. It should be provided in xyz format.
calculate_guesses: Specify whether to calculate the guess wave function only in the first point of the trajectory (“first”) or in all (“all). Here, we keep the default value, first.

In this example, we also show how to further personalize the cp2k_general_settings. In particular, a cp2k subsection is added to overwrite some parameters of the pbe template and tighten the scf convergence criterion to 1e-6 (the default value in the pbe_main template is 5e-4). Please note that a specific indentation is used to reproduce the structure of a typical cp2k input file. By using this approach, you can easily personalize your input requirements by referring to the cp2k manual.

A more elaborate example would have involved the computation of the eigenvalues and energies of orbitals in the triplet state for each point of this singlet trajectory. This would have been done by simply adding multiplicity: 3 under the cp2k_general_settings block.

Setting up the calculation

Once all settings of your yml input have been customized, you are ready to launch your single point calculation.

First, activate the conda environment with QMFlows:

conda activate qmflows
Then, load the module with your version of cp2k, for example:

module load CP2K/7.1.0
Finally, use the command run_workflow.py to submit your calculation:

run_workflow.py -i input_test_single_points_basic.yml

or

run_workflow.py -i input_test_single_points_advanced.yml

for the advanced example.