On the choice of inertial axes for interpreting spectroscopic properties of van der Waals complexes

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Abstract
Properties such as the dipole moments and nuclear quadrupole coupling constants of van der Waals complexes are important in the determination of intermolecular potential energy surfaces from high‐resolution spectra. The properties are often interpreted in terms of angular expectation values. It is shown that, when calculating such properties, it is important to use an inertial axis system that satisfies the Eckart conditions. Projections onto other axes, such as the intermolecular vector or the instantaneous principal axes, can lead to substantial errors when the individual monomers have large moments of inertia.