Van der Waals isomers and ionic reactivity of the cluster system para-chlorofluorobenzene/methanol

C. Riehn, K. Buchhold, B. Reimann, S. Djafari, H. D. Barth, B. Brutschy, P. Tarakeshwar, K. S. Kim

Research output: Contribution to journalArticlepeer-review

36 Scopus citations

Abstract

This combined experimental and computational study is aimed at elucidating the structure and reactivity of heterogeneous molecular clusters. We report results for the system para-chlorofluorobenzene/methanol (pC1FB/MeOH). Particularly, three different van der Waals (vdW) isomers of the neutral (1:1) aggregate (π, σF, σC1) have been assigned by comparison of experimental infrared frequencies in the O-H and C-H stretch regions measured by IR/R2PI depletion spectroscopy with calculated frequencies at MP2/6-31+G(d) and B3LYP/6-31+G(d) level. The isomers are weakly hydrogen-bonded complexes with methanol's OH group coordinated toward the aromatic π-electron cloud, the fluorine or the chlorine substituent, respectively. This assignment is corroborated by the UV and IR spectra of the corresponding monosubstituted benzene/methanol complexes. After resonant photoionization of pClFB-(MeOH)N, for n=1 besides vdW fragmentation, no chemical reactivity was observed for any isomer. The investigation of aggregates with n≥5 indicated a substitution reaction taking place to produce chloroanisole+, emphasizing the importance of neutral precursor cluster size over cluster structure for intracluster ion-molecule reactions.

Original languageEnglish (US)
Pages (from-to)1170-1177
Number of pages8
JournalJournal of Chemical Physics
Volume112
Issue number3
DOIs
StatePublished - Jan 15 2000
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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