Carbenium ions are important intermediates in both zeolite
and
plasma chemistry. The construction of kinetic models for zeolite and
plasma chemistry requires the incorporation of thermodynamic properties
of these carbenium ions. In this way, thermodynamic equilibrium is
incorporated resulting in more accurate and general kinetic models,
which facilitate rational zeolite design and plasma process development.
In this work, a consistent set of 46 group additive values (GAVs)
and non-nearest neighbor interactions (NNIs) is determined for the
standard enthalpy of formation, standard molar entropy, and heat capacity.
The GAVs are regressed based on 165 quantum chemistry calculations
with the CBS-QB3 composite method for carbenium ions as CBS-QB3 was
proven a valid method for carbenium property prediction. The presented
group additive approach gives the first GAVs and NNIs for entropy
and heat capacity and 33 novel values for enthalpy prediction. The
determined non-nearest neighbor interactions account for the effect
of longer range hyperconjugation, resonance stabilization, and inductive
stabilization, which are shown to be crucial for the carbenium stability.
The presented group additivity scheme ensures an accurate prediction
of all properties with a mean absolute error of 4.82 kJ/mol, 4.92
J/(mol·K), and 1.95 J/(mol·K) for the standard enthalpy
of formation, standard molar entropy, and heat capacity, respectively.
The reported GAVs and NNIs ensure the thermodynamic property prediction
of paraffinic, olefinic, alkynic, aromatic, and five- and six-ring
naphthenic cations.