We present a multiscale approach to efficiently embed an ab initio correlated chemical fragment described by its energy-weighted density matrices and entangled with a wider mean-field many-electron system. This approach, first presented by Fertitta and Booth [Phys. Rev. B 98, 235132 (2018)], is here extended to account for realistic long-range interactions and broken symmetry states. The scheme allows for a systematically improvable description in the range of correlated fluctuations out of the fragment into the system, via a self-consistent optimization of a coupled auxiliary mean-field system. It is discussed that the method has rigorous limits equivalent to the existing quantum embedding approaches of both dynamical mean-field theory and density matrix embedding theory, to which this method is compared, and the importance of these correlated fluctuations is demonstrated. We derive a self-consistent local energy functional within the scheme and demonstrate the approach for hydrogen rings, where quantitative accuracy is achieved despite only a single atom being explicitly treated.
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Research Article| July 03 2019
Energy-weighted density matrix embedding of open correlated chemical fragments
Special Collection: Dynamics of Open Quantum Systems
Edoardo Fertitta ;
Edoardo Fertitta, George H. Booth; Energy-weighted density matrix embedding of open correlated chemical fragments. J. Chem. Phys. 7 July 2019; 151 (1): 014115. https://doi.org/10.1063/1.5100290
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