Towards efficient coupled-cluster theories for periodic systems

Tomasz Janowski, Péter Pulay

Ke Liao, Thomas Schraivogel, Hongjun Luo +2 more

We propose a streamlined combination of the transcorrelation (TC) and coupled cluster (CC) theory, which not only increases the convergence rate with respect to the basis set but also extends the applicability of the lowest-order CC approximations to strongly correlated systems. Using the three-dimensional uniform electron gas as a model for real periodic solids and highly accurate ground-state energies from the state-of-the-art quantum Monte Carlo methods as benchmark, we show that, with the correct physical insights incorporated, our TC-CC methods gain drastic improvements in accuracy compared with canonical CC methods, and the errors of our methods remain $\ifmmode\pm\else\textpm\fi{}0.001$ Hartree per electron (Ha/electron) across a wide range of densities. With the greatly improved efficiencies and the balanced and accurate performances at both low and high densities, our methods present great promise for applications on real solids with weak and strong correlations.

Josef Paldus

Tobias Schäfer, Florian Libisch, Georg Kresse +1 more

We present an embedding approach to treat local electron correlation effects in periodic environments. In a single consistent framework, our plane wave based scheme embeds a local high-level correlation calculation [here, Coupled Cluster (CC) theory], employing localized orbitals, into a low-level correlation calculation [here, the direct Random Phase Approximation (RPA)]. This choice allows for an accurate and efficient treatment of long-range dispersion effects. Accelerated convergence with respect to the local fragment size can be observed if the low-level and high-level long-range dispersions are quantitatively similar, as is the case for CC in RPA. To demonstrate the capabilities of the introduced embedding approach, we calculate adsorption energies of molecules on a surface and in a chabazite crystal cage, as well as the formation energy of a lattice impurity in a solid at the level of highly accurate many-electron perturbation theories. The absorption energy of a methane molecule in a zeolite chabazite is converged with an error well below 20 meV at the CC level. As our largest periodic benchmark system, we apply our scheme to the adsorption of a water molecule on titania in a supercell containing more than 1000 electrons.

Isaiah Shavitt, Rodney J. Bartlett

Katelyn Laughon, Jason M. Yu, Tianyu Zhu

We present an efficient implementation of the coupled-cluster Green’s function (CCGF) method for simulating photoemission spectra of periodic systems. We formulate the periodic CCGF approach with Brillouin zone sampling in the Gaussian basis at the coupled-cluster singles and doubles (CCSD) level. To enable CCGF calculations of realistic solids, we propose an active-space self-energy correction scheme by combining CCGF with the cheaper many-body perturbation theory ( GW ) and implement the model order reduction (MOR) frequency interpolation technique. We find that the active-space self-energy correction and MOR techniques significantly reduce the computational cost of CCGF while maintaining the high accuracy. We apply the developed CCGF approaches to compute spectral properties and band structure of silicon (Si) and zinc oxide (ZnO) crystals using triple-ζ Gaussian basis sets and medium-size k -point sampling and find good agreement with experimental measurements.