Ground-State Properties of Crystalline Ice from Periodic Hartree-Fock Calculations and a Coupled-Cluster-Based Many-Body Decomposition of the Correlation Energy

Ground state properties of crystalline ice $Ih$ are investigated by combining periodic Hartree-Fock calculations with a many-body expansion for the electron correlation energy using second-order many-body perturbation theory and coupled-cluster techniques. Very good agreement with experimental data can already be achieved by considering two-body correlation contributions up to the third coordination shell in crystalline ice. This hints at the possibility to accurately simulate ab initio water by using periodic Hartree-Fock calculations together with a parametrized two-body correlation potential.

Figure 1

Ice $Ih$ crystal structure, depicting water dimers (dashed lines) and trimers (solid line), used in the two-body and three-body correlation calculations, respectively.

Figure 2

Lattice energy of ice from HF calculations and various MBPT2 correlation treatments, compared to experiment [37, 38]. Notation: MP2(2,$x$NN) denotes periodic HF calculations plus two-body MBPT2 up to the $x$th shell in nearest neighbors.

Figure 3

Lattice energy of ice from HF calculations and various CCSD($T$) correlation treatments, compared to experiment [37, 38]. For notation see Fig. 2