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We show here that the Hamiltonian for an electronic system may be written exactly in terms of fluctuation operators that transition constituent fragments between internally correlated states, accounting rigorously for inter-fragment electron exchange and charge transfer. Familiar electronic structure approaches can be applied to the renormalized Hamiltonian. For efficiency, the basis for each fragment can be truncated, removing high-energy local arrangements of electrons from consideration, and effectively defining collective coordinates for the fragments. For a large number of problems (especially for non-covalently interacting fragments), this has the potential to fold the majority of electron correlation into the effective Hamiltonian, and it should provide a robust approach to incorporating difficult electronic structure problems into large systems. The number of terms in the exactly transformed Hamiltonian formally scales quartically with system size, but this can be reduced to quadratic in the mesoscopic regime, to within an arbitrary error tolerance. Finally, all but a linear-scaling number of these terms may be efficiently decomposed in terms of electrostatic interactions between a linear-scaling number of pre-computed transition densities. In a companion article, this formalism is applied to an excitonic variant of coupled-cluster theory.
A variant of coupled-cluster theory is described here, wherein the degrees of freedom are fluctuations of fragments between internally correlated states. The effects of intra-fragment correlation on the inter-fragment interaction are pre-computed and
The present work proposes to use density-functional theory (DFT) to correct for the basis-set error of wave-function theory (WFT). One of the key ideas developed here is to define a range-separation parameter which automatically adapts to a given bas
During compression of a water dimer calculated with high-precision first-principles methods, the trends of H-bond and O-H bond lengths show quantum effect of the electronic structure. We found that the H-bond length keeps decreasing, while the O-H bo
Hyperconjugation is a basic conception of chemistry. Its straightforward effect is exhibited by the spatial delocalization characteristics of the electron density distributions or wavefunctions. Such effects on the electron wavefunctions of the highe
We study excitonic states of an atomic impurity in a Fermi gas, i.e., bound states consisting of the impurity and a hole. Previous studies considered bound states of the impurity with particles from the Fermi sea where the holes only formed part of t