Development of multicomponent coupled-cluster method for investigation of multiexcitonic interactions

Abstract: Multicomponent systems are defined as chemical systems that require a quantum mechanical description of two or more different types of particles. Non-Born-Oppenheimer electron-nuclear interactions in molecules, electron-hole interactions in electronically excited nanoparticles, and electron-positron interactions are examples of physical systems that require a multicomponent quantum mechanical formalism. The central challenge in the theoretical treatment of multicomponent systems is capturing the many-body correlation effects that exist not only between particles of identical types (electron-electron) but also between particles of different types (electron-nuclear and electron-hole). In this work, the development and implementation of multicomponent coupled-cluster (mcCC) theory for treating particle-particle correlation in multicomponent systems is presented. This method provides a balanced treatment of many-particle correlation in a general multicomponent system while maintaining a size-consistent and size-extensive formalism. The coupled-cluster ansatz presented here is the extension of the electronic structure CCSD formulation for multicomponent systems and is defined as $\vert \Psi_\mathrm{mcCC} \rangle = e^{T_1^\mathrm{I}+T_2^\mathrm{I}+T_1^\mathrm{II}+T_2^\mathrm{II}+T_{11}^\mathrm{I,II}+T_{12}^\mathrm{I,II}+T_{21}^\mathrm{I,II}+T_{22}^\mathrm{I,II}}\vert 0^\mathrm{I}0^\mathrm{II}\rangle$. The applicability of the mcCC method was demonstrated by computing biexciton binding energies for multiexcitonic systems and benchmarking the results against full configuration interaction calculations. The results demonstrated that connected cluster operators that generate simultaneous excitation in type I and type II space are critical for capturing electron-hole correlation in multiexcitonic systems.