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Nodal Aberration Theory (NAT) was developed to explain the field dependency of aberration field centers in the image plane of nominally rotationally symmetric optical systems that have lost their symmetry through misalignments. A new insight into the theory led to calculating the sigma vectors, which locate the aberration field centers, using the angle between a real-ray trace of the optical axis ray (OAR) and the normal of the local surface where “local” refers to the object and image optical spaces of that surface. Here, we detail the sigma vector calculations for general optical systems and provide an experimental investigation of a misaligned system with a high-precision customized Cassegrain telescope. In the simulations, a Newtonian telescope, a Cassegrain telescope, and a three-mirror anastigmat telescope were misaligned intentionally in ray-tracing software. The sigma vectors were calculated analytically for the third-order aberrations of astigmatism and coma. Experimentally, the same perturbations were implemented for the Cassegrain telescope system, and the aberrations were quantified through interferometric measurements on a grid of field points in the image plane that verified the analytical derivation and simulations.