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, Tarakeshwar Pilarisetty, K. S. Kim

Research output: Contribution to journalArticle

36 Citations (Scopus)

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

Fingerprint

Isomers
Methanol
isomers
methyl alcohol
reactivity
Chemical reactivity
electron clouds
Photoionization
molecular clusters
Fluorine
Chlorine
Benzene
chlorine
fluorine
photoionization
Hydrogen
fragmentation
depletion
Substitution reactions
benzene

ASJC Scopus subject areas

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

Cite this

Riehn, C., Buchhold, K., Reimann, B., Djafari, S., Barth, H. D., Brutschy, B., ... 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. https://doi.org/10.1063/1.480670

Van der Waals isomers and ionic reactivity of the cluster system para-chlorofluorobenzene/methanol. / Riehn, C.; Buchhold, K.; Reimann, B.; Djafari, S.; Barth, H. D.; Brutschy, B.; Pilarisetty, Tarakeshwar; Kim, K. S.

In: Journal of Chemical Physics, Vol. 112, No. 3, 15.01.2000, p. 1170-1177.

Research output: Contribution to journalArticle

Riehn, C, Buchhold, K, Reimann, B, Djafari, S, Barth, HD, Brutschy, B, Pilarisetty, T & Kim, KS 2000, 'Van der Waals isomers and ionic reactivity of the cluster system para-chlorofluorobenzene/methanol', Journal of Chemical Physics, vol. 112, no. 3, pp. 1170-1177. https://doi.org/10.1063/1.480670
Riehn C, Buchhold K, Reimann B, Djafari S, Barth HD, Brutschy B et al. Van der Waals isomers and ionic reactivity of the cluster system para-chlorofluorobenzene/methanol. Journal of Chemical Physics. 2000 Jan 15;112(3):1170-1177. https://doi.org/10.1063/1.480670
Riehn, C. ; Buchhold, K. ; Reimann, B. ; Djafari, S. ; Barth, H. D. ; Brutschy, B. ; Pilarisetty, Tarakeshwar ; Kim, K. S. / Van der Waals isomers and ionic reactivity of the cluster system para-chlorofluorobenzene/methanol. In: Journal of Chemical Physics. 2000 ; Vol. 112, No. 3. pp. 1170-1177.
@article{9312c29e83f24ea28a07d401e004e46d,
title = "Van der Waals isomers and ionic reactivity of the cluster system para-chlorofluorobenzene/methanol",
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.",
author = "C. Riehn and K. Buchhold and B. Reimann and S. Djafari and Barth, {H. D.} and B. Brutschy and Tarakeshwar Pilarisetty and Kim, {K. S.}",
year = "2000",
month = "1",
day = "15",
doi = "10.1063/1.480670",
language = "English (US)",
volume = "112",
pages = "1170--1177",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "3",

}

TY - JOUR

T1 - Van der Waals isomers and ionic reactivity of the cluster system para-chlorofluorobenzene/methanol

AU - Riehn, C.

AU - Buchhold, K.

AU - Reimann, B.

AU - Djafari, S.

AU - Barth, H. D.

AU - Brutschy, B.

AU - Pilarisetty, Tarakeshwar

AU - Kim, K. S.

PY - 2000/1/15

Y1 - 2000/1/15

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0000603319&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000603319&partnerID=8YFLogxK

U2 - 10.1063/1.480670

DO - 10.1063/1.480670

M3 - Article

VL - 112

SP - 1170

EP - 1177

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 3

ER -