Anomalous phosphine sensitivity coefficients as probes for a possible variation of the proton-to-electron mass ratio

A robust variational approach is used to investigate the sensitivity of the rotation-vibration spectrum of phosphine (PH$_3$) to a possible cosmological variation of the proton-to-electron mass ratio, $μ$. Whilst the majority of computed sensitivity coefficients, $T$, involving the low-lying vibrational states acquire the expected values of $T\approx-1$ and $T\approx-1/2$ for rotational and ro-vibrational transitions, respectively, anomalous sensitivities are uncovered for the $A_1\!-\!A_2$ splittings in the $ν_2/ν_4$, $ν_1/ν_3$ and $2ν_4^{\ell=0}/2ν_4^{\ell=2}$ manifolds of PH$_3$. A pronounced Coriolis interaction between these states in conjunction with accidentally degenerate $A_1$ and $A_2$ energy levels produces a series of enhanced sensitivity coefficients. Phosphine is expected to occur in a number of different astrophysical environments and has potential for investigating a drifting constant. Furthermore, the displayed behaviour hints at a wider trend in molecules of ${\bf C}_{3\mathrm{v}}\mathrm{(M)}$ symmetry, thus demonstrating that the splittings induced by higher-order ro-vibrational interactions are well suited for probing $μ$ in other symmetric top molecules in space, since these low-frequency transitions can be straightforwardly detected by radio telescopes.