TY - JOUR
T1 - Statistical Rate Theory Calculations of the Cl-+ CH3Br → ClCH3+ Br- Rate Constant versus Temperature, Translational Energy, and H(D) Isotopic Substitution
AU - Wang, Haobin
AU - Hase, William L.
PY - 1995
Y1 - 1995
N2 - In the work presented here three different statistical theoretical models and three different potential energy surfaces are used to calculate the rate constant for the Cl-+ CH3Br → CICH3 + Br- SN2 nucleophilic substitution reaction versus temperature, relative translational energy and CH3Br temperature, and H(D) isotopic substitution. The calculated rate constants are compared with experimental measurements. In applying one of the theoretical models along with one of the potential energy surfaces, the potential energy for the reaction’s central barrier was chosen by fitting the 300 K Cl- + CH3Br experimental rate constant. Overall, there is poor agreement between the calculated and experimental results. The calculated temperature dependence of the Cl- + CH3Br SN2 rate constant is in qualitative agreement with experiment, but not quantitative. Using anharmonic vibrational frequencies, instead of harmonic, has only a small effect on the rate constant’s calculated temperature dependence. The temperature dependence of the kH/kD isotope effect is fit by one of the theoretical models, microcanonical transition state theory, when using harmonic vibrational frequencies. However, this agreement is dramatically diminished if anharmonic vibrational frequencies are used. Differences between the calculated rate constant versus relative translational energy and CH3Br temperature, i.e., k(Erel,T), and experiment are striking. The decrease in the calculated k(Erel,T), as Erel is increased, is much less pronounced than observed in the experiments. Also, the calculated k(Erel,T) increases as T is increased, while the experimental k(Erel,T) is nearly independent of T. The inability of statistical theories to interpret the kinetics of the Cl- + CH3Br SN2 reaction is in accord with previous theoretical and experimental studies, which indicate the reaction’s dynamics and kinetics is non-statistical.
AB - In the work presented here three different statistical theoretical models and three different potential energy surfaces are used to calculate the rate constant for the Cl-+ CH3Br → CICH3 + Br- SN2 nucleophilic substitution reaction versus temperature, relative translational energy and CH3Br temperature, and H(D) isotopic substitution. The calculated rate constants are compared with experimental measurements. In applying one of the theoretical models along with one of the potential energy surfaces, the potential energy for the reaction’s central barrier was chosen by fitting the 300 K Cl- + CH3Br experimental rate constant. Overall, there is poor agreement between the calculated and experimental results. The calculated temperature dependence of the Cl- + CH3Br SN2 rate constant is in qualitative agreement with experiment, but not quantitative. Using anharmonic vibrational frequencies, instead of harmonic, has only a small effect on the rate constant’s calculated temperature dependence. The temperature dependence of the kH/kD isotope effect is fit by one of the theoretical models, microcanonical transition state theory, when using harmonic vibrational frequencies. However, this agreement is dramatically diminished if anharmonic vibrational frequencies are used. Differences between the calculated rate constant versus relative translational energy and CH3Br temperature, i.e., k(Erel,T), and experiment are striking. The decrease in the calculated k(Erel,T), as Erel is increased, is much less pronounced than observed in the experiments. Also, the calculated k(Erel,T) increases as T is increased, while the experimental k(Erel,T) is nearly independent of T. The inability of statistical theories to interpret the kinetics of the Cl- + CH3Br SN2 reaction is in accord with previous theoretical and experimental studies, which indicate the reaction’s dynamics and kinetics is non-statistical.
UR - http://www.scopus.com/inward/record.url?scp=0000722421&partnerID=8YFLogxK
U2 - 10.1021/ja00141a029
DO - 10.1021/ja00141a029
M3 - Article
AN - SCOPUS:0000722421
SN - 0002-7863
VL - 117
SP - 9347
EP - 9356
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 36
ER -