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We report results on the dynamics of tunnelling switching based on a high-resolution spectroscopic investigation of meta-D-phenol in GHz and THz ranges. The pure rotational spectra were recorded in the range of 72–117 GHz and assigned to the localized syn- and anti-structures in the ground and the first excited torsional states. Specific torsional states were unambiguously assigned by comparison of the experimental rotational constants with theoretical results from quasiadiabatic channel reaction path Hamiltonian (RPH) calculations. The torsional fundamental νT at ≈ 309 cm−1 and the first hot band (2νT – νT) at ≈ 277 cm−1 were subsequently assigned in synchrotron based high-resolution Fourier transform infrared (FTIR, THz) spectra. The analyses provided accurate spectroscopic constants of all six states involved. It was found that the 2νT states are interacting through anharmonic resonances, indicating tunnelling switching as predicted by theory. Furthermore, tunnelling–rotation–vibration transiti...

One-dimensional (1D) and two-dimensional (2D) models are investigated, which help to understand the unusual rovibrational energy-level structure of the astronomically relevant and chemically interesting astructural molecular ion H+5. Due to the very low hindering barrier characterising the 1D torsion-only vibrational model of H+5, this model yields strongly divergent energy levels. The results obtained using a realistic model for the torsion potential, including the computed (near) degeneracies, can be rationalised in terms of the model with no barrier. Coupling of the torsional motion with a single rotational degree of freedom is also investigated in detail. It is shown how the embedding-dependent rovibrational models yield energy levels that can be rationalised via the 2D vibrational model containing two independent torsions. Insight into the complex rovibrational energy level structure of the models and of H+5 is gained via variational nuclear motion and diffusion Monte Carlo computations and by the an...

A hybrid variational–perturbational nuclear motion algorithm based on the perturbative treatment of the Coriolis coupling terms of the Eckart–Watson kinetic energy operator following a variational treatment of the rest of the operator is described. The algorithm has been implemented in the quantum chemical code DEWE. Performance of the hybrid treatment is assessed by comparing selected numerically exact variational vibration-only and rovibrational energy levels of the C2H4, C2D4, and CH4 molecules with their perturbatively corrected counterparts. For many of the rotational–vibrational states examined, numerical tests reveal excellent agreement between the variational and even the first-order perturbative energy levels, whilst the perturbative approach is able to reduce the computational cost of the matrix-vector product evaluations, needed by the iterative Lanczos eigensolver, by almost an order of magnitude.