In this paper, the iteration scheme associated with single reference coupled cluster theory has been analyzed using nonlinear dynamics. The phase space analysis indicates the presence of a few significant cluster amplitudes, mostly involving valence excitations, that dictate the dynamics, while all other amplitudes are enslaved. Starting with a few initial iterations to establish the inter-relationship among the cluster amplitudes, a supervised machine learning scheme with a polynomial kernel ridge regression model has been employed to express each of the enslaved amplitudes uniquely in terms of the former set of amplitudes. The subsequent coupled cluster iterations are restricted solely to determine those significant excitations, and the enslaved amplitudes are determined through the already established functional mapping. We will show that our hybrid scheme leads to a significant reduction in the computational time without sacrificing the accuracy.

The iterative solution of the coupled cluster equations exhibits a synergistic relationship among the various cluster amplitudes. The iteration scheme is analyzed as a multivariate discrete time propagation of nonlinearly coupled equations, which is dictated by only a few principal cluster amplitudes. These principal amplitudes usually correspond to only a few valence excitations, whereas all other cluster amplitudes are enslaved and behave as auxiliary variables [Agarawal et al., J. Chem. Phys. 154, 044110 (2021)]. We develop a coupled cluster–machine learning hybrid scheme where various supervised machine learning strategies are introduced to establish the interdependence between the principal and auxiliary amplitudes on-the-fly. While the coupled cluster equations are solved only to determine the principal amplitudes, the auxiliary amplitudes, on the other hand, are determined via regression as unique functionals of the principal amplitudes. This leads to significant reduction in the number of independent degrees of freedom during the iterative optimization, which saves significant computation time. A few different regression techniques have been developed, which have their own advantages and disadvantages. The scheme has been applied to several molecules in their equilibrium and stretched geometries, and our scheme, with all the regression models, shows a significant reduction in computation time over the canonical coupled cluster calculations without unduly sacrificing the accuracy.