Conservation laws in coupled cluster dynamics at finite temperature

• Published in: The Journal of chemical physics 2021-07, Vol.155 (4)
• Main Authors: Peng, Ruojing, White, Alec F., Zhai, Huanchen, Kin-Lic Chan, Garnet
• Format: Article
• Language: English
• Subjects: astrodynamics; CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; cluster dynamics; coupled-cluster methods; density matrix renormalization group; Ehrenfest theorem; exchange interactions; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; many body problems; many electron systems; operator theory; particle properties
• ISSN: 0021-9606; 1089-7690

We extend the finite-temperature Keldysh non-equilibrium coupled cluster theory (Keldysh-CC) [A. F. White and G. K.-L. Chan, J. Chem. Theory Comput. 15, 6137–6253 (2019)] to include a time-dependent orbital basis. When chosen to minimize the action, such a basis restores local and global conservation laws (Ehrenfest’s theorem) for all one-particle properties while remaining energy conserving for time independent Hamiltonians. We present the time-dependent Keldysh orbital-optimized coupled cluster doubles method in analogy with the formalism for zero-temperature dynamics, extended to finite temperatures through the time-dependent action on the Keldysh contour. To demonstrate the conservation property and understand the numerical performance of the method, we apply it to several problems of nonequilibrium finite-temperature dynamics: a 1D Hubbard model with a time-dependent Peierls phase, laser driving of molecular H2, driven dynamics in warm-dense silicon, and transport in the single impurity Anderson model.