Transcorrelated Random-Phase Approximation

Abstract

We extend the random-phase approximation (RPA) to the non-Hermitian transcorrelated (TC) Hamiltonian, which explicitly includes three-body interactions generated by a Jastrow correlation factor. We consider both the direct RPA (dRPA) and RPA with exchange (RPAx). We apply the resulting TC-dRPA and TC-RPAx methods to calculate ground-state correlation energies and vertical excitation energies for atoms (\ce{He} and \ce{Ne}) and small molecules (\ce{H2O}, \ce{NH3}, \ce{CH4}, and \ce{H2CO}). For ground-state correlation energies, the TC treatment substantially improves accuracy and accelerates basis set convergence, reducing errors by nearly an order of magnitude relative to conventional RPA calculations. By contrast, it yields only marginal improvements in vertical excitation energies. We attribute this limited effect to the ground-state optimization of the Jastrow factor, which does not adequately capture the distinct electronic character of excited states. These results establish TC-RPA as an accurate and computationally efficient approach to ground-state energetics, while highlighting the need for state-specific Jastrow optimization to achieve reliable descriptions of excited states.