Owens, A; Yurchenko, SN; Špirko, V; (2018) Anomalous phosphine sensitivity coefficients as probes for a possible variation of the proton-to-electron mass ratio. Monthly Notices of the Royal Astronomical Society , 473 (4) pp. 4986-4992. 10.1093/mnras/stx2696.

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Abstract

A robust variational approach is used to investigate the sensitivity of the rotation–vibration spectrum of phosphine (PH3) 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 ≈ −1 and T ≈ −1/2 for rotational and ro-vibrational transitions, respectively, anomalous sensitivities are uncovered for the A1 − A2 splittings in the ν2/ν4, ν1/ν3 and 2νℓ=04/2νℓ=24 2ν4ℓ=0/2ν4ℓ=2 manifolds of PH3. A pronounced Coriolis interaction between these states in conjunction with accidentally degenerate A1 and A2 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 C3v(M) C3v(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.

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