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 journalArticle

36 Scopus citations


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
Issue number3
StatePublished - Jan 15 2000
Externally publishedYes

ASJC Scopus subject areas

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

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    Riehn, C., Buchhold, K., Reimann, B., Djafari, S., Barth, H. D., Brutschy, B., Tarakeshwar, P., & Kim, K. S. (2000). Van der Waals isomers and ionic reactivity of the cluster system para-chlorofluorobenzene/methanol. Journal of Chemical Physics, 112(3), 1170-1177.