A quantum theory of thermal reaction rates is presented which may be viewed as an extension of the recently developed "quantum instanton" (QI) model [W. H. Miller, Y. Zhao, M. Ceotto, and S. Yang, J. Chem. Phys. 119, 1329 (2003)]. It is based on using higher derivatives of the flux-flux autocorrelation function C(t) (as given by Miller, Schwartz, and Tromp) at t = 0 to construct a short time approximation for C(t). Tests of this theory on 1d and collinear reactions, both symmetric and asymmetric, show it to be more accurate than the original QI model, giving rate constants to ~5% for a wide range of temperature.
Quantum reaction rate from higher derivatives of the thermal flux-flux autocorrelation function at time zero / M. Ceotto, S. Yang, W.H. Miller. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 122:4(2005 Jan 22), pp. 044109.1-044109.7.
Quantum reaction rate from higher derivatives of the thermal flux-flux autocorrelation function at time zero
M. Ceotto;
2005
Abstract
A quantum theory of thermal reaction rates is presented which may be viewed as an extension of the recently developed "quantum instanton" (QI) model [W. H. Miller, Y. Zhao, M. Ceotto, and S. Yang, J. Chem. Phys. 119, 1329 (2003)]. It is based on using higher derivatives of the flux-flux autocorrelation function C(t) (as given by Miller, Schwartz, and Tromp) at t = 0 to construct a short time approximation for C(t). Tests of this theory on 1d and collinear reactions, both symmetric and asymmetric, show it to be more accurate than the original QI model, giving rate constants to ~5% for a wide range of temperature.File | Dimensione | Formato | |
---|---|---|---|
Ceotto_05_higherderivativesQI.pdf
accesso riservato
Tipologia:
Publisher's version/PDF
Dimensione
132.74 kB
Formato
Adobe PDF
|
132.74 kB | Adobe PDF | Visualizza/Apri Richiedi una copia |
Pubblicazioni consigliate
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.