westerfit: A new program for spin–torsion–rotation spectra

Abstract

A new program, westerfit, has been developed to treat $C_s$ molecules with internal rotation and spin angular momentum. It implements a single diagonalization Rho Axis Method approach for the torsion–rotation alongside a complete treatment of nuclear quadrupole interaction and spin–rotation coupling. Unlike other programs designed for internal rotation with spin effects, westerfit includes matrix elements off-diagonal in the rotational angular momentum quantum number, $N$, rather than the perturbative treatment of the spin–rotation and quadrupole interactions. This full combined approach allows fitting of all symmetrically allowed terms in both the spin–rotation and the quadrupole tensors as well as inclusion of higher order terms coupling the large amplitude motion to the spin angular momentum. The program was benchmarked against other published programs to test molecular cases of torsion–rotation, spin–rotation, and spin–torsion-rotation. All three tests produced a lower RMS. westerfit paves a way forward for complete treatment of spin–torsion–rotation problems regardless of barrier height or quadrupole moment.