Potential energy surfaces, quasiadiabatic channels, rovibrational spectra, and intramolecular dynamics of (HF)2 and its isotopomers from quantum Monte Carlo calculations

We report analytical representations of the six‐dimensional potential energy hypersurface for (HF)2, the parameters of which are closely adjusted to low energy experimental properties such as hydrogen bond dissociation energy (D0=1062 cm−1 ) and vibrational–rotational spectra in the far and mid infrared. We present a detailed analysis of properties of the hypersurface in terms of its stationary points, harmonic normal mode amplitudes, and frequencies for the Cs minimum and C2h saddle point and effective Morse parameters and anharmonic overtone vibrational structure for the hydrogen bond and the HF stretching vibrations. The comparison between experimental data and the potential energy surface is carried out by means of accurate solutions of the rotational–vibrational Schrodinger equation with quantum Monte Carlo techniques, which include anharmonic interactions between all modes for the highly flexible dimer. Two extensions of the quantum Monte Carlo technique are presented, which are based on the clamped...

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