Abstract
We present a theoretical study of the effect of reagent vibrational excitation on cross sections and rate constants for the reactions H + HCN (v1v2v3) → H2 + CN and H + N2O(V1v2v3) → N2 + OH, NH + NO. For H + HCN, we study the states (000), (004) and (302), and we find that C-H stretch excitation is much more effective than C-N stretch in lowering the reactive threshold energy and thus enhancing the rate constant. For H + N2O we study the states (000), (100), (0110) and (001). Here N-N stretch excitation is more effective in enhancing the cross section at low energy where the reaction mechanism involves HNNO complex formation. At higher energy (3.3 kcal/mol above threshold and higher), N-O stretch excitation is more effective in enhancing the reaction cross section, due to the dominance of a direct mechanism involving a NN-O-H transition state.
| Original language | English |
|---|---|
| Pages (from-to) | 144-154 |
| Number of pages | 11 |
| Journal | Springer Series in Chemical Physics |
| Volume | 61 |
| Publication status | Published - 1996 |
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- Physical and Theoretical Chemistry
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Mode-specific chemistry in the H + HCN and H + N2O reactions. / Ter Horst, M.; Bradley, K. S.; Schatz, George C.
In: Springer Series in Chemical Physics, Vol. 61, 1996, p. 144-154.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Mode-specific chemistry in the H + HCN and H + N2O reactions
AU - Ter Horst, M.
AU - Bradley, K. S.
AU - Schatz, George C
PY - 1996
Y1 - 1996
N2 - We present a theoretical study of the effect of reagent vibrational excitation on cross sections and rate constants for the reactions H + HCN (v1v2v3) → H2 + CN and H + N2O(V1v2v3) → N2 + OH, NH + NO. For H + HCN, we study the states (000), (004) and (302), and we find that C-H stretch excitation is much more effective than C-N stretch in lowering the reactive threshold energy and thus enhancing the rate constant. For H + N2O we study the states (000), (100), (0110) and (001). Here N-N stretch excitation is more effective in enhancing the cross section at low energy where the reaction mechanism involves HNNO complex formation. At higher energy (3.3 kcal/mol above threshold and higher), N-O stretch excitation is more effective in enhancing the reaction cross section, due to the dominance of a direct mechanism involving a NN-O-H transition state.
AB - We present a theoretical study of the effect of reagent vibrational excitation on cross sections and rate constants for the reactions H + HCN (v1v2v3) → H2 + CN and H + N2O(V1v2v3) → N2 + OH, NH + NO. For H + HCN, we study the states (000), (004) and (302), and we find that C-H stretch excitation is much more effective than C-N stretch in lowering the reactive threshold energy and thus enhancing the rate constant. For H + N2O we study the states (000), (100), (0110) and (001). Here N-N stretch excitation is more effective in enhancing the cross section at low energy where the reaction mechanism involves HNNO complex formation. At higher energy (3.3 kcal/mol above threshold and higher), N-O stretch excitation is more effective in enhancing the reaction cross section, due to the dominance of a direct mechanism involving a NN-O-H transition state.
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M3 - Article
VL - 61
SP - 144
EP - 154
JO - Springer Series in Chemical Physics
JF - Springer Series in Chemical Physics
SN - 0172-6218
ER -