Watching a hydroperoxyalkyl radical (•QOOH) dissociate

Abstract

Carbon-centered radicals containing the hydroperoxy group, commonly denoted as •QOOH, are elusive but are among the most critical intermediate species for kinetic modeling of hydrocarbon oxidation in various atmospheric and combustion processes. Their direct experimental observation is a long-standing challenge, with only one successful previous attempt. Using a combination of infrared activation spectroscopy and an ultraviolet laser–induced fluorescence detection method, Hansen et al . directly characterized the vibrational structure of a •QOOH intermediate in isobutane oxidation, collisionally stabilized and isolated, and followed its dissociative evolution under infrared activation with time and energy resolution. High-level electronic structure calculations revealed an important role of heavy-atom tunneling in this process. —YS

Document Details

Document Type
Pub Defense Publication
Publication Date
Aug 06, 2021
Source ID
10.1126/science.abj0412

Entities

People

  • Ahren W Jasper
  • Anne S. Hansen
  • Daniel R Moberg
  • Kevin B Moore
  • Marsha I. Lester
  • Michael F Vansco
  • Stephen Klippenstein
  • Trisha Bhagde
  • Yuri Georgievskii

Organizations

  • Argonne National Laboratory
  • Army Research Office
  • Carlsberg Foundation
  • Independent Research Fund Denmark
  • National Science Foundation
  • United States Department of Energy
  • University of Pennsylvania

Tags

Fields of Study

  • Chemistry

Readers

  • Molecular Photonics/Laser Physics
  • Organic Chemistry
  • Quantum Chemistry

Technology Areas

  • Directed Energy
  • Microelectronics