Well converged quantum rate constants for the H2+ OH → H2O + H reaction via transition state wave packet

2018 ◽  
Vol 149 (6) ◽  
pp. 064303 ◽  
Author(s):  
Peng Sun ◽  
Zhaojun Zhang ◽  
Jun Chen ◽  
Shu Liu ◽  
Dong H. Zhang
Keyword(s):  
Wave Packet ◽  
Transition State ◽  
Rate Constants ◽  
State Wave

Cumulative isomerization probability studied by various transition state wave packet methods including the MCTDH algorithm. Benchmark: HCN→CNH isomerization

2004 ◽  
Vol 121 (2) ◽  
pp. 644-654 ◽  
Author(s):  
B. Lasorne ◽  
F. Gatti ◽  
E. Baloitcha ◽  
H.-D. Meyer ◽  
M. Desouter-Lecomte
Keyword(s):  
Wave Packet ◽  
Transition State ◽  
State Wave

Transition state wave packet study of hydrogen diffusion on Cu(100) surface

1999 ◽  
Vol 111 (13) ◽  
pp. 5741-5753 ◽  
Author(s):  
Dong H. Zhang ◽  
John C. Light ◽  
Soo-Y. Lee
Keyword(s):  
Wave Packet ◽  
Transition State ◽  
Hydrogen Diffusion ◽  
State Wave

A transition state wave packet study of the H+CH4 reaction

2007 ◽  
Vol 127 (23) ◽  
pp. 234313 ◽  
Author(s):  
Liling Zhang ◽  
Yunpeng Lu ◽  
Soo-Y. Lee ◽  
Dong H. Zhang
Keyword(s):  
Wave Packet ◽  
Transition State ◽  
State Wave

Diffusion of a hydrogen atom on the Pd(111) surface: quantum transition state wave packet approach

2003 ◽  
Vol 547 (1-2) ◽  
pp. 149-156 ◽  
Author(s):  
I. Nikitin ◽  
W. Dong ◽  
H.F. Busnengo ◽  
A. Salin
Keyword(s):  
Hydrogen Atom ◽  
Wave Packet ◽  
Transition State ◽  
Quantum Transition ◽  
State Wave

Effect of Medium on Reactivity for Alkaline Hydrolysis of p-Nitrophenyl Acetate and S-p-Nitrophenyl Thioacetate in DMSO-H2O Mixtures of Varying Compositions: Ground State and Transition State Contributions

2021 ◽  
Author(s):  
Ik-Hwan Um ◽  
Seungjae Kim
Keyword(s):  
Transition State ◽  
Alkaline Hydrolysis ◽  
Ground State ◽  
Rate Constants ◽  
Kinetic Data ◽  
Reaction Medium ◽  
Stepwise Mechanism ◽  
Rate Determining Step ◽  
Leaving Group ◽  
Hydrolysis Of

Second-order rate constants (kN) for reactions of p-nitrophenyl acetate (1) and S-p-nitrophenyl thioacetate (2) with OH‒ have been measured spectrophotometrically in DMSO-H2O mixtures of varying compositions at 25.0 ± 0.1 oC. The kN value increases from 11.6 to 32,800 M‒1s‒1 for the reactions of 1 and from 5.90 to 190,000 M‒1s‒1 for those of 2 as the reaction medium changes from H2O to 80 mol % DMSO, indicating that the effect of medium on reactivity is more remarkable for the reactions of 2 than for those of 1. Although 2 possesses a better leaving group than 1, the former is less reactive than the latter by a factor of 2 in H2O. This implies that expulsion of the leaving group is not advanced in the rate-determining transition state (TS), i.e., the reactions of 1 and 2 with OH‒ proceed through a stepwise mechanism, in which expulsion of the leaving group from the addition intermediate occurs after the rate-determining step (RDS). Addition of DMSO to H2O would destabilize OH‒ through electronic repulsion between the anion and the negative-dipole end in DMSO. However, destabilization of OH‒ in the ground state (GS) is not solely responsible for the remarkably enhanced reactivity upon addition of DMSO to the medium. The effect of medium on reactivity has been dissected into the GS and TS contributions through combination of the kinetic data with the transfer enthalpies (ΔΔHtr) from H2O to DMSO-H2O mixtures for OH‒ ion.

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