Issue 38, 2024

Infrared-driven dynamics and scattering mechanisms of NO radicals with propane and butane: impacts of pseudo Jahn–Teller effects

Abstract

The topology of multidimensional potential energy surfaces defines the bimolecular collision outcomes of open–shell radicals with molecular partners. Understanding these surfaces is crucial for predicting the inelastic scattering and chemical transformations of increasingly complex radical–molecule collisions. To characterize the inelastic scattering mechanisms of nitric oxide (NO) radicals with large alkanes, we generated the collision complexes comprised of NO with propane or n-butane. The infrared action spectroscopy and infrared-driven dynamics of NO–propane and NO–(n-butane) collision complexes in the CH stretch region were recorded, while also comparing the results to the analogous experiments carried out for NO–CH4 and NO–ethane. The infrared spectroscopy is analyzed using rovibrational simulations to characterize the transition bands and to determine the vibrational predissociation lifetimes of NO–propane and NO–(n-butane). Due to pseudo Jahn–Teller dynamics, the NO–propane and NO–(n-butane) decay mechanisms from IR activation appear similar to those for NO–ethane previously reported from this laboratory (J. P. Davis et al. Faraday Discuss., 2024, 251, 262–278). Furthermore, the NO (X2Π, v′′ = 0, J′′, Fn, Λ) product state distributions from NO–alkane fragmentation reveal a strong electron-spin polarization and a propensity for NO products to rotate in the plane of the π* molecular orbital, yielding mechanistic insights into the inelastic scattering outcomes. We hypothesize that a geometric phase may be present, impacting the relative population distributions, in addition to the accessible pathway timescales.

Graphical abstract: Infrared-driven dynamics and scattering mechanisms of NO radicals with propane and butane: impacts of pseudo Jahn–Teller effects

Supplementary files

Article information

Article type
Paper
Submitted
02 Jun 2024
Accepted
10 Sep 2024
First published
18 Sep 2024

Phys. Chem. Chem. Phys., 2024,26, 24849-24860

Infrared-driven dynamics and scattering mechanisms of NO radicals with propane and butane: impacts of pseudo Jahn–Teller effects

P. G. Burroughs, W. C. Wilkinson, E. Majumdar, J. D. Bole, R. Subedi, J. T. Kerrigan and N. M. Kidwell, Phys. Chem. Chem. Phys., 2024, 26, 24849 DOI: 10.1039/D4CP02254H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements