Communication: General variational approach to nuclear-quadrupole coupling in rovibrational spectra of polyatomic...

A general algorithm for computing the quadrupole-hyperfine effects in the rovibrational spectra of polyatomic molecules is presented for the case of ammonia (NH₃). The method extends the general variational approach TROVE [J. Mol. Spectrosc. 245, 126-140 (2007)] by adding the extra term in the Hamiltonian that describes the nuclear quadrupole coupling, with no inherent limitation on the number of quadrupolar nuclei in a molecule. We applied the new approach to compute the nitrogen-nuclear-quadrupole hyperfine structure in the rovibrational spectrum of NH314. These results agree very well with recent experimental spectroscopic data for the pure rotational transitions in the ground vibrational and ν₂ states and the rovibrational transitions in the ν₁, ν₃, 2ν₄, and ν₁ + ν₃ bands. The computed hyperfine-resolved rovibrational spectrum of ammonia will be beneficial for the assignment of experimental rovibrational spectra, further detection of ammonia in interstellar space, and studies of the proton-to-electron mass variation.