Tunneling in the loss of hydrogen chloride from isopropyl chloride cation

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Abstract

The unimolecular dissociation of isopropyl chloride cation has been investigated using mass-analyzed ion kinetic energy spectrometry. The C 3H6+ ion was the only product ion in the metastable dissociation. The kinetic energy release distribution for the HCl loss was determined. Ab initio molecular orbital calculations were performed at the MP2/6-311++G(d,p) level together with single point energy calculations at the QCSID-(T)/6-311++G(2d,2p) level. The calculations show that the molecular ion rearranges to an ion-dipole complex prior to loss of HCl via a transition state containing a four-membered ring. The rearrangement involves H atom transfer. On the basis of the potential energy surface obtained for the loss of HC1 and Cl, the rate constants were calculated by transition-state statistical theories with considering tunneling effect. From the calculated result, it is proposed that the observed HC1 loss would occur via tunneling through the barrier for isomerization to the ion-dipole complex, CH3CHCH 2+⋯HCl.

Original languageEnglish
Pages (from-to)4979-4984
Number of pages6
JournalJournal of Physical Chemistry A
Volume110
Issue number15
DOIs
StatePublished - 20 Apr 2006

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