skip to main content

DOE PAGESDOE PAGES

This content will become publicly available on December 1, 2018

Title: Time-Resolved Kinetic Chirped-Pulse Rotational Spectroscopy in a Room-Temperature Flow Reactor

Chirped-pulse Fourier transform millimeter-wave spectroscopy is a potentially powerful tool for studying chemical reaction dynamics and kinetics. Branching ratios of multiple reaction products and intermediates can be measured with unprecedented chemical specificity; molecular isomers, conformers, and vibrational states have distinct rotational spectra. Here we demonstrate chirped-pulse spectroscopy of vinyl cyanide photoproducts in a flow tube reactor at ambient temperature of 295 K and pressures of 1-10 mu bar. This in situ and time-resolved experiment illustrates the utility of this novel approach to investigating chemical reaction dynamics and kinetics. Following 193 nm photodissociation of CH2CHCN, we observe rotational relaxation of energized HCN, HNC, and HCCCN photoproducts with 10 mu s time resolution and sample the vibrational population distribution of HCCCN. The experimental branching ratio HCN/HCCCN is compared with a model based on RRKM theory using high-level ab initio calculations, which were in turn validated by comparisons to Active Thermochemical Tables enthalpies.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 24; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Branching ratio; Chemical reaction dynamics and kinetics; Gas phase; HC3N; Rotational relaxation and equilibration; Vibrational level population distribution
OSTI Identifier:
1426235