Files in this item

FilesDescriptionFormat

application/vnd.openxmlformats-officedocument.presentationml.presentation

application/vnd.openxmlformats-officedocument.presentationml.presentation1064667.pptx (8MB)
PresentationMicrosoft PowerPoint 2007

application/pdf

application/pdf2901.pdf (19kB)
AbstractPDF

Description

Title:PROPYLBENZENE-(H2O)n CLUSTERS: EFFECT OF THE ALKYL CHAIN ON THE π H-BOND
Author(s):Mishra, Piyush
Contributor(s):Zwier, Timothy S.; Sibert, Edwin; Fischer, Joshua L.
Subject(s):Clusters/Complexes
Abstract:This talk focuses on the mass resolved- resonant 2-photon ionization (R2PI), resonant ion-dip infrared spectroscopy (RIDIR) and IR-UV holeburning (IR-UV HB) spectroscopy of propylbenzene(pBz)-(\chem{H_2O})$_{n}$ clusters and the comparison with their Benzene(Bz)-(\chem{H_2O})$_{n}$ cluster counterparts, which are a well-studied prototype system for the $\pi$ H-bond. Since the pBz monomer exists in \textit{gauche} and \textit{trans} conformers, one anticipates the presence of pBz-\chem{H_2O} complexes with \chem{H_2O} on the same or opposite sides of the ring as the \textit{gauche} or \textit{trans} propyl chain. Indeed, local minima associated with these four complexes were identified by dispersion-corrected DFT calculations. R2PI and IR-UV HB spectra of pBz-\chem{H_2O} show long Franck-Condon progressions associated with the set of conformers of the complex. The OH stretch RIDIR spectra consist of a single transition in the symmetric stretch region, and a doublet with varying spacing in the antisymmetric stretch region, indicating coupling to a large-amplitude motion (LAM). The changes in the OH stretch region indicate that the water molecule bound to propylbenzene undergoes more restricted motion on the $\pi$ cloud than its Bz-\chem{H_2O} counterpart. The potential energy surface for \chem{H_2O} tumbling on the pBz $\pi$ cloud was mapped out, and used as the basis for calculating from first principles the OH stretch infrared spectrum. Comparison with the spectrum for Bz-\chem{H_2O} further illustrates the source and restrictions of the LAM of \chem{H_2O} in pBz compared to Bz. OH stretch IR spectra of the higher water clusters pBz-(\chem{H_2O})$_{n}$ with n=3, 4 are very similar to their Bz-(\chem{H_2O})$_{n}$ counterparts, existing as H-bonded cycles, with no evidence of LAM on the aromatic $\pi$ cloud.
Issue Date:06/19/18
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:APS
Genre:Conference Paper / Presentation
Type:Text
Language:English
URI:http://hdl.handle.net/2142/100810
DOI:10.15278/isms.2018.TE09
Other Identifier(s):TE09
Date Available in IDEALS:2018-08-17
2018-12-12


This item appears in the following Collection(s)

Item Statistics