Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments

The photodissociation dynamics of roaming in formaldehyde are studied by comparing quasi-classical trajectory calculations performed on a new potential energy surface (PES) to new and detailed experimental results detailing the CO + H2 product state distributions and their correlations. The new PES...

Full description

Saved in:
Bibliographic Details
Published in:The Journal of chemical physics 2017-07, Vol.147 (1), p.013936-013936
Main Authors: Houston, Paul L., Wang, Xiaohong, Ghosh, Aryya, Bowman, Joel M., Quinn, Mitchell S., Kable, Scott H.
Format: Article
Language:English
Subjects:
Correlation
Formaldehyde
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Internal energy
Mathematical analysis
Photodissociation
Potential energy
Rotational states
Trajectories
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The photodissociation dynamics of roaming in formaldehyde are studied by comparing quasi-classical trajectory calculations performed on a new potential energy surface (PES) to new and detailed experimental results detailing the CO + H2 product state distributions and their correlations. The new PES proves to be a significant improvement over the past one, now more than a decade old. The new experiments probe both the CO and H2 products of the formaldehyde dissociation. The experimental and trajectory data offer unprecedented detail about the correlations between internal states of the CO and H2 dissociation products as well as information on how these distributions are different for the roaming and transition-state pathways. The data investigated include, for dissociation on the formaldehyde 2143 band, (a) the speed distributions for individual vibrational/rotational states of the CO products, providing information about the correlated internal energy distributions of the H2 product, and (b) the rotational and vibrational distributions for the CO and H2 products as well as the contributions to each from both the transition state and roaming channels. The agreement between the trajectory and experimental data is quite satisfactory, although minor differences are noted. The general agreement provides support for future use of the experimental techniques and the new PES in understanding the dynamics of photodissociative processes.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4982823