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 language | English (US) |
|---|---|
| Pages (from-to) | 1170-1177 |
| Number of pages | 8 |
| Journal | Journal of Chemical Physics |
| Volume | 112 |
| Issue number | 3 |
| DOIs | |
| State | Published - Jan 15 2000 |
| Externally published | Yes |
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry