Quantum Rotation of HCN and DCN in Helium-4

Abstract

We present calculations of rotational absorption spectra of the molecules HCN and DCN in superfluid helium-4, using a combination of the Diffusion Monte Carlo method for ground state properties and an analytic many-body method (Correlated Basis Function theory) for the excited states. Our results agree with the experimentally determined effective moment of inertia which has been obtained from the $J=0\to 1$ spectral transition. The correlated basis function analysis shows that, unlike heavy rotors such as OCS, the J=2 and higher rotational excitations of HCN and DCN have high enough energy to strongly couple to rotons, leading to large shifts of the lines and accordingly to anomalous large spectroscopic distortion constants, to the emergence of roton-maxon bands, and to secondary peaks in the absorption spectra for J=2 and J=3.

accepted by Phys. Rev. B; changes: included referee suggestions, removed typos, added 10 refs