Interface to PCMSolver by R. Di Remigio

Code author: Roberto Di Remigio, T. Daniel Crawford, Andrew C. Simmonett

Section author: Roberto Di Remigio

Module: Keywords, PSI Variables, PCMSolver

PSI4 contains code to interface to the PCMSolver library developed by R. Di Remigio and L. Frediani. The PCMSolver library requires no additional licence, downloads, or configuration. The library allows for calculations in solution with the polarizable continuum model (PCM), a continuum solvation model [Tomasi:2005:2999].

Installation

Binary

• 

• PCMSolver is available as a conda package for Linux and macOS (and Windows, through the Ubuntu shell).

• If using the PSI4 binary, PCMSolver has already been installed alongside.

• If using PSI4 built from source, and anaconda or miniconda has already been installed (instructions at Quick Installation), PCMSolver can be obtained through conda install pcmsolver -c psi4. Then enable it as a feature with ENABLE_PCMSolver, hint its location with CMAKE_PREFIX_PATH, and rebuild PSI4 to detect PCMSolver and activate dependent code.

• To remove a conda installation, conda remove pcmsolver.

Source

• 

• If using PSI4 built from source and you want PCMSolver built from from source also, enable it as a feature with ENABLE_PCMSolver, and let the build system fetch and build it and activate dependent code.

Using the polarizable continuum model

The inclusion of a PCM description of the solvent into your calculation can be achieved in two ways in PSI4, using either the PCMSolver or ddx package. PCMSolver is based on a boundary-element discretisation [Cances:1998:309], while ddx is based on a domain decomposition approach [Cances:2013:054111] making it linear scaling. For more details about ddx see the section on ddx.

Using PCMsolver is achieved instead by setting PCM true in your input file. PSI4 understands the additional option PCM_SCF_TYPE with possible values total (the default) or separate. The latter forces the separate handling of nuclear and electronic electrostatic potentials and polarization charges. It is mainly useful for debugging.

For the calculation of vertical excitation energies with PCM non-equilibrium solvation should be included with:

pcm = {
   Medium {
   Nonequilibrium = True
   }
}

Note

At present PCM can only be used for energy calculations with SCF wavefunctions and CC wavefunctions in the PTE approximation [Cammi:2009:164104]. All ERI algorithms (PK, OUT_OF_CORE, DIRECT, DF, CD) are supported.

Note

linear response calculations (static polarisabilities, TD-SCF) are supported for RHF/UHF if available.

Warning

The PCMSolver library cannot exploit molecular point group symmetry.

Warning

ROHF with PCM is known not to work. See issue #999 on GitHub. For the adventurous, a fix is available in pull request #953 on GitHub

Warning

Analytic gradients and Hessians are not available with PCM. Finite differences will be used regardless of the dertype passed to the optimize function. See pcmsolver/opt-fd for a sample input.

The PCM model and molecular cavity are specified in a pcm section that has to be explicitly typed in by the user. This additional section follows a syntax that is slightly different from that of PSI4 and is fully documented here

A typical input for a Hartree–Fock calculation with PCM would look like the following:

molecule NH3 {
symmetry c1
N     -0.0000000001    -0.1040380466      0.0000000000
H     -0.9015844116     0.4818470201     -1.5615900098
H     -0.9015844116     0.4818470201      1.5615900098
H      1.8031688251     0.4818470204      0.0000000000
units bohr
no_reorient
no_com
}

set {
  basis STO-3G
  scf_type pk
  pcm true
  pcm_scf_type total
}

pcm = {
   Units = Angstrom
   Medium {
   SolverType = IEFPCM
   Solvent = Water
   }

   Cavity {
   RadiiSet = UFF
   Type = GePol
   Scaling = False
   Area = 0.3
   Mode = Implicit
   }
}

More examples can be found in the directories with PCM tests pcmsolver/ccsd-pte, pcmsolver/scf, pcmsolver/opt-fd, pcmsolver/dft, and pcmsolver/dipole.

Keywords for PCMSolver

PCM

PCM boolean for pcmsolver module

• Type: boolean

• Default: false

PCM_SCF_TYPE

Use total or separate potentials and charges in the PCM-SCF step.

• Type: string

• Possible Values: TOTAL, SEPARATE

• Default: TOTAL

PCM_CC_TYPE

PCM-CCSD algorithm type.

• Type: string

• Possible Values: PTE

• Default: PTE

How to configure PCMSolver for building Psi4

Role and Dependencies

• Role — In PSI4, PCMSolver is a library that provides additional quantum chemical capabilities (solvation modeling).

• Downstream Dependencies — PSI4 (\(\Leftarrow\) optional) PCMSolver

• Upstream Dependencies — PCMSolver \(\Leftarrow\) Fortran, zlib

CMake Variables

• ENABLE_PCMSolver — CMake variable toggling whether Psi4 builds with PCMSolver

• CMAKE_PREFIX_PATH — CMake list variable to specify where pre-built dependencies can be found. For PCMSolver, set to an installation directory containing include/PCMSolver/pcmsolver.h

• PCMSolver_DIR — CMake variable to specify where pre-built PCMSolver can be found. Set to installation directory containing share/cmake/PCMSolver/PCMSolverConfig.cmake

• CMAKE_DISABLE_FIND_PACKAGE_PCMSolver — CMake variable to force internal build of PCMSolver instead of detecting pre-built

• CMAKE_INSIST_FIND_PACKAGE_PCMSolver — CMake variable to force detecting pre-built PCMSolver and not falling back on internal build

Examples

1. Build bundled

>>> cmake -DENABLE_PCMSolver=ON

2. Build without PCMSolver

>>> cmake