Finite Temperature Coupled Cluster Theories for Extended Systems.

Abstract

At zero temperature, coupled cluster theories are widely used to predict total energies, ground state expectation values, and even excited states for molecules and extended systems. However, for systems with a small band gap, such as metals, the zero-temperature approximation does not necessarily hold. Thermal effects may even give rise to interesting chemistry on metal surfaces. Most approaches to temperature dependent electronic properties employ finite temperature perturbation theory in the Matsubara frequency formulation. Computations require a large number of Matsubara frequencies to yield sufficiently accurate results, especially at low temperatures. This work, and independently the work of White and Chan J. Chem. Theory Comput. 2018 , DOI: 10.1021/acs.jctc.8b00773 , proposes a coupled cluster implementation directly in the imaginary time domain on the compact interval [0, β], closely related to the thermal cluster cumulant approach of Sanyal et al. [ Chem. Phys. Lett. 1992 , 192 , 55 - 61 ] , Sanyal et al. [ Phys. Rev. E 1993 , 48 , 3373 - 3389 ], and Mandal et al. [ Int. J. Mod. Phys. B 2003 , 17 , 5367 - 5377 ]. Here, the arising imaginary time dependent coupled cluster amplitude integral equations are solved in the linearized direct ring doubles approximation, also referred to as Tamm-Dancoff approximation with second order (linearized) screened exchange. In this framework, the transition from finite to zero temperature is uniform and comes at no extra costs, allowing to go to temperatures as low as room temperature. In this approximation, correlation grand potentials are calculated over a wide range of temperatures for solid lithium, a metallic system, and for solid silicon, a semiconductor.