Dynamics of Formation of Products D₂CN⁺, DCN⁺, and CD₃⁺ in the Reaction of N⁺ with CD₄: A Crossed-Beam and Theoretical Study

Abstract

The formation of D(2)CN(+) in the reaction of N(+) ((3)P) with CD(4) was studied using the crossed beam technique at collision energies of 3.66 and 4.86 eV. The experiments were complemented by calculations of stationary points on the triplet hypersurface of the system. The scattering data showed that the reaction proceeds by the formation of two intermediate complexes having different lifetimes: a long-lived statistical intermediate and a short-lived complex (mean lifetime about one period of an average rotation) with more energy in translation than the statistical complex. Comparison with theoretical calculations suggests that the long-lived complex leads the CDND(+) isomer of the product ion, whereas the short-lived complex leads prevailingly to the CD(2)N(+) isomer. The product DCN(+) results from further decomposition of the primary product D(2)CN(+), whereas CD(3)(+) is formed both by a hydride-ion transfer and a long-lived complex decomposition.

Dynamics of the Water Dimer + Nitric Oxide Collision

“…However, some complexes undergo two rotations. The numbers are in general comparable with the findings of other short‐ to medium‐life complex systems . We note that the ensemble‐averaged angles listed above suggest that NO is near the donor monomer when energy transfer takes place; see Figure .…”

Selected Ion Flow Tube Study of Ion–Molecule Reactions of N+(3P) and Kr+ with C3 Hydrocarbons Propane, Propene, and Propyne

“…( n = 8, 6, 4) normalN + false( normalP 3 false) + normalC 3 normalH italicn false( false) 1 → normalC 3 normalH italicn + false( false) 2 + normalN false( normalS 4 false) and possibly reactions of hydride-ion transfer, e.g. 6 N + ( P 3 ) + C 3 H n ( ) 1 → C 3 H n − 1 + ( ) 1 + NH ( normalX Σ 3 ) followed by further dissociation of the primary H – transfer product. A contribution of chemical reactions in which the nitrogen atom is embedded into the ion product, as observed earlier in collisions with methane, e.g …”

“… a Reaction enthalpies, −Δ R H , in eV. Bold numbers indicate exothermic processes. b N b : the three numbers refer to N in the ground state, N( 4 S) and in the excited states N b ( 2 D) and N b ( 2 P), respectively; E exc ( 2 D) = 2.38 eV, E exc ( 2 P) = 3.58 eV. c NH: the two numbers refer to NH in the triplet states, in the ground state(X 3 Σ) and in the excited state (A 3 Π), respectively, E exc (A 3 Π) = 3.70 eV. d Assumed structures (see text for discussion). e Assuming triplet states of the products HCNH + and HCN + …”

“…This is presumably an excited state lying above the singlet ground state. In a very rough analogy with the singletÀtriplet separation in CHNH þ , 11 this state may be located about 4 eV above the ground state and the respective exothermicity should be by about 4 eV smaller than the value given in Table 1 (À4.8 eV). The fraction of N-containing ions is about 15% of all product ions formed.…”

“…In studies of the system N + + CH 4 (CD 4 ) information on rate constants and branching ratios were obtained from ICR, , SIFT, , and drift tube-mass spectrometric experiments. Further details were obtained from product luminescence, , reactant state selection, and crossed-beam studies . Studies of reactions between N + and C 2 hydrocarbons involved reactions with acetylene, ethylene, and ethane.…”