Anharmonic vibrational spectroscopy calculations for (NH3)(HF) and (NH3)(DF): fundamental, overtone, and combination...

In order to study the effects of hydrogen bonding on the spectroscopic properties of (NH3)(HF) and (NH3)(DF) complexes, vibrational spectra (including fundamental, overtone and combination transitions) were calculated using the vibrational self consistent field (VSCF) method. This ab initio VSCF method accounts for both one-dimensional anharmonicity and pair-wise mode-mode couplings for all vibrational modes of the molecule, using points on the potential energy surface (at the MP2/TZP level of theory in this study). An analysis of the coupling strength shows surprisingly important coupling effects from pair-wise interactions not expected to be major. This indicates the benefits of including all pair-wise mode-mode couplings for weakly bound systems. Hydrogen bonding induces approximately 20% red shifts for the HF and DF stretch frequencies. The corrections due to anharmonicity for these modes are -6% and -5%, respectively. The anharmonic corrections for the intermolecular stretch of (NH3)(HF) and (NH3)(DF) are each about -5%. The NH3 umbrella motion has virtually no anharmonic correction in the complex, whereas free ammonia experiences a -15% correction. Also, the closing motion as well as the opening motion is restricted. The 1 + 1 combination transition of the proton stretching and intermolecular stretching modes has remarkably large intensity, larger even than the intensities for the first overtone of the proton stretching modes. The anharmonic frequency for the fundamental HF stretch, 3268 cm(-1), is in good agreement with the experimental gas phase result, 3215 cm(-1). A comparison to solid rare-gas matrix data shows that the VSCF frequencies are a consistent improvement over the harmonic approximation. The experimental data also support the use of the MP2 level of theory for the associated electronic structure calculations.