TY - JOUR
T1 - Relationship between mode specific and thermal unimolecular rate constants for HOCL → OH + Cl dissociation
AU - Song, Kihyung
AU - Sun, Lipeng
AU - Hase, William L.
AU - Grebenshchikov, S. Yu
AU - Schinke, Reinhard
PY - 2002/9/12
Y1 - 2002/9/12
N2 - Recent quantum dynamical calculations [Hauschildt, J.; et al. Chem. Phys. Lett. 1999, 300, 569] have shown that HOCl → OH + Cl dissociation on the ground-state potential energy surface, and for J = 0, occurs predominantly via isolated compound-state resonances, whose rates are highly mode-specific. In this work, these resonance rates are averaged to calculate the HOCl → OH + Cl unimolecular rate constant as a function of temperature and pressure. The result is compared with the standard pressure and temperature dependent RRKM unimolecular rate constant. It is found that the state-specificity makes the pressure-dependent rates significantly lower than the RRKM rates in the intermediate pressure regime.
AB - Recent quantum dynamical calculations [Hauschildt, J.; et al. Chem. Phys. Lett. 1999, 300, 569] have shown that HOCl → OH + Cl dissociation on the ground-state potential energy surface, and for J = 0, occurs predominantly via isolated compound-state resonances, whose rates are highly mode-specific. In this work, these resonance rates are averaged to calculate the HOCl → OH + Cl unimolecular rate constant as a function of temperature and pressure. The result is compared with the standard pressure and temperature dependent RRKM unimolecular rate constant. It is found that the state-specificity makes the pressure-dependent rates significantly lower than the RRKM rates in the intermediate pressure regime.
UR - http://www.scopus.com/inward/record.url?scp=0037068881&partnerID=8YFLogxK
U2 - 10.1021/jp014689l
DO - 10.1021/jp014689l
M3 - Article
AN - SCOPUS:0037068881
VL - 106
SP - 8339
EP - 8344
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 36
ER -