Loss of HCN from the Pyrimidine Molecular Ion: A Computational Study

Loss of HCN from the Pyrimidine Molecular Ion: A Computational Study

The potential energy surface (PES) for the loss of HCN from the pyrimidine molecular ion has been explored using quantum chemical calculations. Possible reaction pathways to form five $C_3H_3N^{+{\bullet}}$ isomers have been obtained with Gaussian 4 model calculations. The rate constant for the HCN loss and the product branching ratio have been calculated using the Rice-Ramsperger-Kassel-Marcus theory on the basis of the obtained PES. The resultant rate constant agrees with the previous experimental result. By a kinetic analysis, it is proposed that the formation of $CH=CHC{\equiv}NH^{+{\bullet}}$ is favored near the dissociation threshold, while the formation of $CH=CHN{\equiv}CH^{+{\bullet}}$ is favored at high energies.