Gaseous Cl3+ and Cl2F+ cations.: A joint mass spectrometric and theoretical study

The Cl-3(+) cation was obtained by chlorine chemical ionization (Cl-2/Cl) via the exothermic reaction of Cl+ transfer from Cl2H+ to chlorine or by the endothermic reaction of Cl-2(+.) with chlorine, whereas Cl2F+ was obtained from the reaction of XeF+ with chlorine. Both cations were structurally and energetically characterized by Fourier transform ion cyclotron resonance mass spectrometry and theoretical calculations at the B3LYP/6-311++G(3df,3pd)// CCSD(T)/cc-pVQZ levels of theory. (C) 1998 John Wiley & Sons, Ltd.