Attaining high accuracy for charge-transfer excitations in non-covalent complexes at second-order perturbation cost: The importance of state-specific self-consistency.

Abstract

Intermolecular charge-transfer (xCT) excited states important for various practical applications are challenging for many standard computational methods. It is highly desirable to have an affordable method that can treat xCT states accurately. In the present work, we extend our self-consistent perturbation methods, named one-body second-order Møller-Plesset and its spin-opposite scaling variant (O2BMP2), for excited states without additional costs to the ground state. We then assessed their performance for the prediction of xCT excitation energies. Thanks to self-consistency, our methods yield small errors relative to high-level coupled cluster methods and outperform other same scaling (N5) methods, such as CC2 and ADC(2). In particular, O2BMP2, whose scaling can be reduced to N4, can even reach the accuracy of CC3 (N7) with errors less than 0.1 eV. This method is thus highly promising for treating xCT states in large compounds vital for applications.