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Abstract
Comparisons are presented of experimental and theoretical studies of the rotationally inelastic scattering of CD3 radicals with H2 and D2 collision partners at respective collision energies of 680 +/ 75 and 640 +/ 60 cm(1). Closecoupling quantummechanical calculations performed using a newly constructed ab initio potential energy surface (PES) provide initialtofinal CD3 rotational level (n, k > n', k') integral and differential cross sections (ICSs and DCSs). The DCSs are compared with crossed molecular beam and velocity map imaging measurements of angular scattering distributions, which serve as a critical test of the accuracy of the new PES. In general, there is very good agreement between the experimental measurements and the calculations. The DCSs for CD3 scattering from both H2 and D2 peak in the forward hemisphere for n' = 24 and shift more to sideways and backward scattering for n' = 5. For n' = 68, the DCSs are dominated by backward scattering. DCSs for a particular CD3 n > n' transition have a similar angular dependence with either D2 or H2 as collision partner. Any differences between DCSs or ICSs can be attributed to mass effects because the PES is unchanged for CD3H2 and CD3D2 collisions. Further comparisons are drawn between the CD3D2 scattering and results for CD3He presented in our recent paper [O. Tkac, A. G. Sage, S. J. Greaves, A. J. OrrEwing, P. J. Dagdigian, Q. Ma, and M. H. Alexander, Chem. Sci. 4, 4199 (2013)]. These systems have the same reduced mass, but are governed by different PESs. (C) 2014 AIP Publishing LLC.
Original language  English 

Article number  204318 
Number of pages  12 
Journal  Journal of Chemical Physics 
Volume  140 
Issue number  20 
DOIs  
Publication status  Published  30 May 2014 
Bibliographical note
Accepted 13/05/2014Keywords
 BASISSETS
 MOLECULARBEAM
 MULTIPHOTON IONIZATION
 QUANTUM SCATTERING
 ENERGYTRANSFER
 RIGIDROTOR
 AR
 HE
 COLLISIONS
 EXCITATION
Projects
 1 Finished

NEW HORIZONS IN CHEMICAL AND PHOTOCHEMICAL DYNAMICS
OrrEwing, A. J. & Ashfold, M. N. R.
1/10/08 → 1/04/14
Project: Research