Correlated Product Distributions in the Photodissociation of à State NO-CH 4and NO-N 2van der Waals Complexes

Heather L. Holmes-Ross, Jason R. Gascooke, Warren D. Lawrance

Research output: Contribution to journalArticlepeer-review


This paper reports correlated product distributions for dissociation of the van der Waals complexes NO-CH 4and NO-N 2on their A state surfaces, providing detailed data sets against which calculations can be benchmarked. NO-CH 4dissociation strongly favors small changes in the CH 4angular momentum, with ΔJ = 0 and 1 providing the bulk of the products. Conversely, the associated NO products show little constraint in terms of the rotational angular momentum transfer, with the full range of energetically accessible angular momentum states populated, although the distributions show minima. The lack of angular momentum transfer to methane accompanied by broad, structured, angular momentum transfer to NO gives the NO-CH 4dissociation some qualitative similarities to NO-Rg complex dissociation. In contrast, for NO-N 2, the cluster of highest probability products corresponds to high N 2angular momentum and low NO angular momentum, with a sharp drop in the probability for populating the highest energetically accessible J states. For both the NO and N 2products, there appears to be a constraint limiting angular momentum transfer at the highest energetically accessible rotational states. Both complexes show product distributions that include a component attributed to excitation from warm complexes, which provides insight into their internal energies. Interestingly, for NO-N 2, the 44,475 cm -1photolysis translational energy release distribution for N = 8 extends to energies beyond those accessible from the highest bound X states. This indicates either that there are long-lived (>100 μs) states above the X state binding energy or that there is another mechanism that also contributes to this distribution.

Original languageEnglish
Pages (from-to)7981–7996
Number of pages16
JournalJournal of Physical Chemistry A
Issue number43
Publication statusPublished - 3 Nov 2022


  • van der Waals complexes
  • correlated product distributions
  • data sets
  • NO–CH4
  • NO–N2
  • Ã state surfaces
  • X̃ states


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