Files in this item

FilesDescriptionFormat

application/pdf

application/pdfGregory_Pullen_ISMS_2019.pdf (3MB)
PresentationPDF

application/pdf

application/pdf3947.pdf (18kB)
AbstractPDF

application/vnd.openxmlformats-officedocument.presentationml.presentation

application/vnd.openxmlformats-officedocument.presentationml.presentation1448549.pptx (8MB)
PresentationMicrosoft PowerPoint 2007

Description

Title:TUNNELING REACTIONS OF HYDROGEN ADDITION TO PROPENE IN A SOLID PARA-HYDROGEN MATRIX
Author(s):Pullen, Gregory T.
Contributor(s):Lee, Yuan-Pern ; Haupa, Karolina Anna; Douberly, Gary E.; Franke, Peter R.
Subject(s):Comparing theory and experiment
Abstract:We report the branching ratio for the H + propene tunneling reaction to form \textit{n}- or \textit{i}-propyl radicals within a solid \textit{para}-hydrogen (\textit{p}-\chem{H_2}) matrix at 3.2 K. Chlorine and propene are co-deposited in the \textit{p}-\chem{H_2} matrix, and then 365 nm and infrared light sources are used to produce HCl and free H atoms. These free H atoms can tunnel through the matrix until they encounter a propene molecule, at which point they can react to form either an \textit{n}-propyl or an \textit{i}-propyl radical. \textit{i}-Propyl was produced in greater proportion than \textit{n}-propyl, indicating that for hydrogen addition to the double bond, the rate of addition to the terminal carbon (\textit{i}-propyl) is faster than the rate of addition to the center carbon (\textit{n}-propyl). Because the barriers for addition are approximately 700 cm$^{-1}$ – 1500 cm$^{-1}$ (1000 K – 2000 K), the only available mechanism for reaction in the \textit{p}-\chem{H_2} matrix (3.2 K) is tunneling. \textit{Ab initio} calculations were used to compute the tunneling probabilities for the formation of the \textit{n}-propyl and \textit{i}-propyl radicals. The rate of addition to the terminal carbon (\textit{i}-propyl) was calculated to be faster, in agreement with experiment.
Issue Date:2019-06-21
Publisher:International Symposium on Molecular Spectroscopy
Genre:Conference Paper / Presentation
Type:Text
Language:English
URI:http://hdl.handle.net/2142/104382
DOI:10.15278/isms.2019.FF08
Rights Information:Copyright 2019 Gregory T. Pullen
Date Available in IDEALS:2019-07-15
2020-01-25


This item appears in the following Collection(s)

Item Statistics