Towards black-box calculations of tunneling splittings obtained from vibrational structure methods based on normal coordinates

摘要

Multidimensional potential energy surfaces obtained from explicitly correlated coupled-cluster calculations and further corrections for high-order correlation contributions, scalar relativistic effects and corecorrelation energy contributions were generated in a fully automated fashion for the double-minimum benchmark systems OH_3~+ and NH_3. The black-box generation of the potentials is based on normal coordinates, which were used in the underlying multimode expansions of the potentials and the l-tensor within the Watson operator. Normal coordinates are not the optimal choice for describing double-minimum potentials and the question remains if they can be used for accurate calculations at all. However, their unique definition is an appealing feature, which removes remaining errors in truncated potential expansions arising from different choices of curvilinear coordinate systems. Fully automated calculations are presented, which demonstrate, that the proposed scheme allows for the determination of energy levels and tunneling splittings as a routine application.