Improved Description of Charge-Transfer Potential Energy Surfaces via Spin-Component-Scaled CC2 and ADC(2) Methods

摘要

The molecular level understanding of electronic transport properties depends on the reliable theoretical description of charge-transfer (CT)-type electronic states. In this paper, the performance of spin-component-scaled variants of the popular CC2 and ADC(2) methods is evaluated for CT states, following benchmark strategies of earlier studies that revealed a compromised accuracy of the unmodified models. In addition to statistics on the accuracy of vertical excitation energies at equilibrium and infinite separation of bimolecular complexes, potential energy surfaces of the ammonia–fluorine complex are also reported. The results show the capability of spin-component-scaled approaches to reduce the large errors of their regular counterparts to a significant extent, outperforming even the coupled-cluster single and double method in many cases. The cost-effective scaled-opposite-spin variants are found to provide a remarkably good agreement with the CCSDT-3 reference data, thereby being recommended methods of choice in the study of charge-transfer states.