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 (pClFB/MeOH). Particularly, three different van der Waals (vdW) isomers of the neutral (1:1) aggregate (π,σF,σCl) 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.

Resonance-enhanced multiphoton ionization (REMPI) spectroscopy of p–chlorofluorobenzene

“…The origin transition was analysed via UV absorption spectroscopy by Cvitaš and Hollas [14], but the most pertinent is a resonance-enhanced multiphoton ionization (REMPI) study from Numata et al [15] to which we shall refer to further in the below; however, we note that only band position wavenumbers were given, but no assignments. There has also been a REMPI study of the pClFBmethanol complex by Riehn et al [16], but that of the monomer was not presented.…”

Ab InitioStudy on Structures and Vibrational Spectra of M+(H2O)Ar2(M = Cu, Au)

“…Since the full BSSE correction often tends to underestimate the binding energies for small and midsize basis sets, while 50%-BSSE-corrected value, which should be used with caution, may be closer to the experimental values [36,37]. The 50%-BSSEcorrection is employed in the present paper.…”

Utilization of an aspiration thrombectomy catheter (Pronto) to treat acute atherothrombotic embolization during percutaneous revascularization of the lower extremity

“…The basis set superposition error (BSSE) is accounted for by using counterpoise procedure of Boys and Bernardi 44 in the interaction energy calculations of the noble‐gas‐noble‐metal bonds. Since the full BSSE correction often tends to underestimate binding energies for small and midsize basis sets, while 50%‐BSSE‐corrected value, which should be used with caution, may be closer to the experimental value 47–50. Hence 50%‐BSSE‐correction is also employed here.…”