Spin-Component-Scaled ΔMP2 Parametrization: Toward a Simple and Reliable Method for Ionization Energies.

A practical, accurate, and cost- and implementation-free method (ΔMP2-SOS(IP)) for the calculation of vertical ionization potentials is proposed. The simple method is based on a single-step, a diagonal, frequency-independent approximation to the second-order self-energy expression combined with the spin-component-scaled technique. The search for an optimal scaling factor is performed for a set of 50 moderately sized molecules, and the quality of the method is additionally assessed for a benchmark set of 24 organic acceptor molecules. The proposed ΔMP2-SOS(IP) method provides the best results of valence ionization energies as compared to the several standard self-consistent variants of the electron propagator methods at the second and higher orders (EP2, SCS-EP2, EP3, OVGF) with almost CCSD(T) or IP-EOM-CCSD accuracy and the cost of only a single opposite-spin ΔMP2-type calculation ( O( N3)). For core ionization energies, our new methods outperform the standard ΔMP2 results due to a better balanced treatment of the correlation and relaxation term in the second-order self-energy.