Polarizable continuum model: some basic remarks

The possibility to perform solvent calculations is currently under development in the pcm branch. We will exploit a Continuum Solvation Model (CSM) namely the Polarizable Continuum Model (PCM). PCM is a focused model: the solute (a single molecule or a cluster containing the solute and some relevant solvent molecules) is described quantum mechanically, while the solvent is approximated as a structureless continuum whose interaction with the solute is mediated by its permittivity, \(\varepsilon\) .

The solute is accomodated inside a molecular cavity, built as a set of interlocking spheres centered on the atoms constituting the molecule under investigation. The current implementation in DIRAC is limited to an SCF description of the solute. For a more in-depth presentation of the PCM, please refer to [Tomasi2005], [Mennucci2007] and references therein. For a presentation of the details of the implementation in DIRAC, please refer to [DiRemigio2015].

Basic Theory

In CSMs we write the Schrödinger equation for the solute as:

\begin{equation*} \left[ H_0 + V_{\sigma\rho}(\rho_{\mathrm{M}})\right] | \psi \rangle = E | \phi \rangle \end{equation*}

where \(H_0\) is the solute Hamiltonian in vacuo and \(V_{\sigma\rho}(\rho_{\mathrm{M}})\) is the solute-solvent interaction potential, which depends on the solute wavefunction through the first-order density matrix. This introduces a nonlinearity which must be dealt with appropriately. In standard molecular electronic-structure theory we write the energy as the expectation value of the Hamiltonian (\(| \phi \rangle\) being a trial wave function):

\begin{equation*} \langle \phi | H_0 | \phi \rangle \end{equation*}

An upper-bound estimate to the exact energy of the system can then be obtained by a variational procedure from this functional. When introducing a nonlinearity of the type above, the standard functional does not lead to an upper-bound estimate to the exact energy upon minimization. The appropriate functional is instead given by:

\begin{equation*} \langle \phi | H_0 + \frac{1}{2}V_{\sigma\rho} | \phi \rangle \end{equation*}

which has the status of a free energy (an extensive justification of this fact is given in [Tomasi1994]).

Thus in the PCM framework, the basic energetic quantity is the free energy of solvation which is conveniently partitioned as follows ([Mennucci2007], [Tomasi2005], [Amovilli1998]):

\begin{equation*} \Delta G_\mathrm{sol} = \Delta G_\mathrm{el} + G_\mathrm{cav} + G_\mathrm{dis} + G_\mathrm{rep} + \Delta G_\mathrm{Mm} \end{equation*}

where:

  • \(\Delta G_\mathrm{el}\) accounts for the electrostatic solute-solvent interaction, arising from mutual polarization in the charge distributions;
  • \(G_\mathrm{cav}\) is the cavitation energy, needed to form the molecular cavity inside the continuum representing the solvent;
  • \(G_\mathrm{dis}\) is the dispersion energy, due to the solute-solvent dispesion interactions;
  • \(G_\mathrm{rep}\) is the repulsion energy, which accounts for Pauli repulsioni;
  • \(\Delta G_\mathrm{Mm}\) is due to molecular motion and accounts for entropic contributions to the free energy.

The electrostatic term is, usually, the largest contribution to the solvation energy. Thus we will exclusively be concerned with its calculation (see also [Amovilli1998] for a discussion of the other terms).

Warning

The non-electrostatic terms are not implemented in DIRAC.

In CSMs the calculation of this term requires the solution of the classical Poisson problem nested within the QM calculation. We will define the expectation value of the solvent operator \(V_{\sigma\rho}\) as the polarization energy:

\begin{equation*} U_\mathrm{pol} = \langle \psi | V_{\sigma\rho} | \psi \rangle \end{equation*}

Electrostatic term in the Polarizable Continuum Model

In the PCM, the solute-solvent electrostatic interaction is represented by an apparent surface function (ASC) \(\sigma\) spread on the cavity surface. Using the integral equation formulation of the Poisson problem, the apparent surface charge is obtained by solving an appropriate integral equation relating \(\sigma\) to the molecular electrostatic potential (MEP) \(\varphi\) evaluated on the cavity surface:

\begin{equation*} \mathcal{T}(\varepsilon_\mathrm{r})\sigma = -\mathcal{R}\varphi \end{equation*}

The integral operators \(\mathcal{T}(\varepsilon_\mathrm{r})\) and \(\mathcal{R}\) are defined as follows:

\begin{equation*} \mathcal{T}(\varepsilon_\mathrm{r}) = \left(2\pi\frac{\varepsilon + 1}{\varepsilon_r -1} - \mathcal{D}\right)\mathcal{S} \end{equation*}
\begin{equation*} \mathcal{R} = 2\pi - \mathcal{D} \end{equation*}

in terms of components of the Calderon projector (see [Tomasi2005]) This equation can be solved numerically by discretization of the cavity surface with a triangular mesh (the finite elements being called tesserae). The solution of the electrostatic problem then amounts to solving a linear system of equations:

\begin{equation*} \mathbf{T}\mathbf{q} = -\mathbf{R}\mathbf{v} \rightarrow \mathbf{q} = \mathbf{K}\mathbf{v} \end{equation*}

where \(\mathbf{v}\) and \(\mathbf{q}\) are vectors of dimension equal to the number of finite elements. They contain the MEP and the ASC, respectively, sampled at the finite elements centroids. The polarization energy can be expressed as the scalar product of the MEP and ASC sampled at the cavity boundary:

\begin{equation*} U_\mathrm{pol} = \mathbf{q}\cdot\mathbf{v} \end{equation*}

If we split the MEP into its nuclear and electronic parts \(\mathbf{v} = \mathbf{v}^\mathrm{N} + \mathbf{v}^\mathrm{e}\) , due to the linearity of Poisson equation, the same separation can be achieved for the ASC \(\mathbf{q} = \mathbf{q}^\mathrm{N} + \mathbf{q}^\mathrm{e}\) . Exploiting this separation the polarization energy can be rewritten as:

\begin{equation*} U_\mathrm{pol} = U_\mathrm{NN} + U_\mathrm{Ne} + U_\mathrm{eN} + U_\mathrm{ee} = U_\mathrm{NN} + 2U_\mathrm{eN} + U_\mathrm{ee} \end{equation*}

where \(U_{xy} (x, y = \mathrm{e}, \mathrm{N})\) is the interaction energy between the \(x\) charge distribution and the \(y\) -induced ASC. We also exploited the self-adjointedness of \(\mathbf{K}\) to get \(U_\mathrm{Ne} = U_\mathrm{eN}\) .

PCM-SCF

Nesting the PCM inside an SCF calculation requires the calculation of the MEP and ASC at cavity points at every SCF iteration and the update of the Fock matrix to account for the effect of the mutual solute-solvent polarization. The “solvated” Fock matrix is written as:

\begin{equation*} f_{pq}= f_{pq}^\mathrm{vac} + \mathbf{q}\cdot\mathbf{v}_{pq}^\mathrm{e} \end{equation*}

The PCM matrix elements are more explicitly given as:

\begin{equation*} \mathbf{q}\cdot\mathbf{v}_{pq}^\mathrm{e} = \sum_{I}^{N_\mathrm{ts}}q_Iv_{pq,I}^\mathrm{e} \end{equation*}
\begin{equation*} v_{pq,I}^\mathrm{e} = \left\langle \phi_p \left| \frac{-1}{|\mathbf{r} - \mathbf{s}_I|} \right| \phi_q \right\rangle \end{equation*}