PMID- 16451025
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20070628
LR  - 20060202
IS  - 1089-5639 (Print)
IS  - 1089-5639 (Linking)
VI  - 110
IP  - 5
DP  - 2006 Feb 9
TI  - Isopropylcyclopropane + OH gas phase reaction: a quantum chemistry + CVT/SCT 
      approach.
PG  - 1917-24
AB  - A theoretical study of the mechanism and kinetics of the OH hydrogen abstraction 
      from isopropylcyclopropane (IPCP) is presented. Optimum geometries, frequencies 
      and gradients have been computed at the BHandHLYP/6-311++G(d,p) level of theory 
      for all stationary points, as well as for additional points along the minimum 
      energy path (MEP). Energies have been improved by single-point calculations at 
      the above geometries using CCSD(T)/6-311++G(d,p) to produce the potential energy 
      surface. The rate coefficients are calculated for the temperature range 260-350 K 
      by using canonical variational theory (CVT) with small-curvature tunneling (SCT) 
      corrections. Our analysis suggests a stepwise mechanism involving the formation 
      of a reactant complex in the entrance channel and a product complex in the exit 
      channel, for all the modeled paths. The reactant complexes are examined in 
      detail, because they exhibit alkene-like structure. The excellent agreement 
      between the overall calculated and experimental rate coefficients at 298 K 
      supports the reliability of the parameters obtained for the temperature 
      dependence and branching ratios of the IPCP + OH reaction, proposed here for the 
      fist time. The expression that best describes the studied reaction is k(overall) 
      = 6.15 x 10(-13)e1747/RT cm3 x molecule(-1) x s(-1). The predicted activation 
      energy is -0.89 kcal/mol.
FAU - Galano, Annia
AU  - Galano A
AD  - Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico D. 
      F., Mexico. agalano@imp.mx
FAU - Cruz-Torres, Armando
AU  - Cruz-Torres A
FAU - Alvarez-Idaboy, J Raul
AU  - Alvarez-Idaboy JR
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Phys Chem A
JT  - The journal of physical chemistry. A
JID - 9890903
EDAT- 2006/02/03 09:00
MHDA- 2006/02/03 09:01
CRDT- 2006/02/03 09:00
PHST- 2006/02/03 09:00 [pubmed]
PHST- 2006/02/03 09:01 [medline]
PHST- 2006/02/03 09:00 [entrez]
AID - 10.1021/jp056117x [doi]
PST - ppublish
SO  - J Phys Chem A. 2006 Feb 9;110(5):1917-24. doi: 10.1021/jp056117x.