## Files in this item

FilesDescriptionFormat

application/vnd.openxmlformats-officedocument.presentationml.presentation

1064667.pptx (8MB)
PresentationMicrosoft PowerPoint 2007

application/pdf

2901.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: 2018-08-172018-12-12
﻿