Computational analysis of the proton‐bound acetonitrile dimer, (ACN)₂H⁺

Abstract

Rationale:In atmospheric pressure ionization mass spectrometry the theoretical thermodynamic treatment of proton-bound cluster stabilities helps us to understand the prevailing chemical processes. However, such calculations are rather challenging because low-barrier internal rotations and strong anharmonicity of the hydrogen bonds cause the breakdown of the usually applied harmonic approximation. Even the implemented anharmonic treatment in standard ab initio software failed in the case of (ACN) 2 H + .Methods: For a case study of the proton-bound acetonitrile dimer, (ACN) 2 H + , we scan the potential energy surface (PES) for the internal rotation and the proton movement in all three spatial directions. We correct the partition functions by treating the internal rotation as a free rotor and by solving the nuclear Schrödinger equation explicitly for the proton movement. An additional PES scan for the dissociation surface further improves the understanding of the cluster behavior. Results:The internal rotation is essentially barrier free (V 0 = 2.6 × 10 −6 eV) and the proton's movement between the two nitrogen atoms follows a quartic rather than quadratic potential. As a figure of merit we calculate the free dissociation enthalpy of the dimer. Our description significantly improves the standard results from about 118.3 kJ/mol to 99.6 kJ/mol, compared with the experimentally determined value of 92.2 kJ/mol. The dissociation surface reveals strong crosstalk between modes and is essentially responsible for the observed errors. Conclusions:The presented corrections to the partition functions significantly improve their accuracy and are rather easy to implement. In addition, this work stresses the importance of alternative theoretical methods for proton-bound cluster systems besides the standard harmonic approximations.