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

doi:10.1063/1.480670

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

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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, σ_F, σ_C1) 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	https://doi.org/10.1063/1.480670
State	Published - Jan 15 2000
Externally published	Yes

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General Physics and Astronomy
Physical and Theoretical Chemistry

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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 P. Tarakeshwar and Kim, {K. S.}",

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language = "English (US)",

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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 - Tarakeshwar, P.

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.

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

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