Ab initio study of the decomposition of formamidine

The decomposition of formamidine yielding hydrogen cyanide and ammonia has been investigated by ab initio calculations. Optimized geometries for reactants, transition states, and products were determined at the HF/6-31G(d) and MP2/6-31G(d) levels of theory. Energies were also determined at the G1, G2, G2MP2, G3, G3B3, G3MP2, and G3MP2B3 levels of theory. The role of water in the decomposition reaction of formamidine was examined. Intrinsic reaction coordinate (IRC) analysis was carried out for all transition states. Activation energies, enthalpies and free energies of activation were also calculated for each reaction pathway. G3 level of theory predicts the gas-phase decomposition of formamidine to have a high activation energy of 259.1 kJ mol–1. Adding one water molecule catalyses the reaction by forming a cyclic hydrogen-bonded transition state, reducing the barrier to 169.4 kJ mol–1 at the G3 level. Addition of a second water, which acts as a "solvent" molecule, further reduces the barrier to 151.1 kJ mol–1 at the G3 level. These values are still high and explain why rather extreme conditions are necessary to achieve this reaction experimentally. Thermodynamic properties (ΔE, ΔH, and ΔG) for each reaction pathway studied were also calculated. The G3 heats of reaction (ΔE) of the gas-phase decomposition of formamidine, its complex with one water molecule, and its complex with two water molecules are 0.9, 2.2, and –5.1 kJ mol –1, respectively. The G3 heat of reaction for the gas-phase decomposition to yield separated products is 22.3 kJ mol–1. Free energies of reaction and of activation in aqueous solution were calculated with PCM using the KLAMT cavity model. At MP2 the formamidine reaction is found to be exergonic in aqueous solution and to favour formation of the separated products (NH3 + HCN). The solvent model predicts a significant lowering of the free energy of activation (16–18 kJ mol–1) for the unimolecular reaction and 21–42 kJ mol–1 for the water-mediated reaction in aqueous solution relative to the gas phase. Key words: decomposition reaction, formamidine, Hartree–Fock, post Hartree–Fock, Gaussian-n theories, IRC, solvation models, PCM, KLAMT.