Quantum chemical analysis of possible fragmentation of [M + H]+ and [M + Na]+ complexes of monosubstituted methane, cyclohexane, and benzene derivatives in mass spectrometric studies

Abstract

The formation and fragmentation energies of the proton and sodium cation complexes with monosubstituted methane, cyclohexane, and benzene derivatives in which carbon atoms are bonded to substituents (NH2, OH, F, Cl, Br, ONO2, NO2, COOH, CN, and Ph) were calculated by the B3LYP/6-31G(d) method. For [M + Na]+ complexes, the formation energies are much lower (and differ from one another to a much lesser extent), while the dissociation energies are much higher, than the corresponding energies of the [M + H]+ complexes. Na+ cation shows a lower selectivity toward localization at functional groups in molecules compared to H+.