Transition state theory with Tsallis statistics

نویسندگان

  • Wolfgang Quapp
  • Alraune Zech
چکیده

We discuss the rate of an elementary chemical reaction. We use the reaction path and especially its saddle point on the potential energy surface. The reaction path connects reactant and product of a reaction over the transition state (TS). Usually, the TS is assumed near or at the single saddle point of the reaction path. By means of comparison of the statistics of states at the reactant and at the TS, one can estimate the reaction rate by the Eyring theory. We propose to use the Tsallis statistics at the TS, a statistics of seldom accidents. Thus, we propose to generalize the well-known Boltzmann-Gibbs statistics, which is the limiting case of the Tsallis statistics. We use features of this nonextensive thermostatistics. The basic properties of the statistics are used to derive (approximated) partition functions, and they are applied on reaction rates. The approximation includes a factorization of the partition functions. The theory is applied to HCN isomerization to HNC, and to the reaction H(2) + CN --> H + HCN. It allows an accordance with experimental estimations of the reaction rates.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Universality of First and Second Order Phase Transition in Solar Activity: Evidence for Nonextensive Tsallis Statistics

In this work, we present the coexistence of self-organized criticality (SOC) and low-dimensional chaos at solar activity with results obtained by using the intermittent turbulence theory, the nonextensive q-statistics of Tsallis as well as the singular value decomposition analysis. Particularly, we show the independent dynamics of sunspot system related to the convection zone of sun and the sol...

متن کامل

3 Comment on “ Nonextensive hamiltonian systems follow Boltzmann ’ s principle not Tsallis statistics - phase transition , second law of thermodynamics ” by Gross

Recently, Gross claims that Boltzmann entropy S = k lnW is valid for any system at equilibrium, so that Tsallis entropy is useless in this case. I comment on some arguments forwarded to reach this conclusion and argue that the additive energy formalism of nonextensive statistics is not appropriate for the fundamental study of the theory for nonadditive systems. PACS : 02.50.-r, 05.20.-y, 05.30....

متن کامل

Comment on “ Nonextensive hamiltonian systems follow Boltzmann ’ s principle not Tsallis statistics - phase transition , second law of thermodynamics ” by Gross

Recently, Gross claims that Boltzmann entropy S = k lnW is valid for any system at equilibrium, so that Tsallis entropy is useless in this case. I comment on some arguments forwarded to reach this conclusion and argue that the additive energy formalism dominating nonextensive statistics is not appropriate for the fundamental study of the theory for nonadditive systems. PACS : 02.50.-r, 05.20.-y...

متن کامل

Hydrogen Abstraction Reaction of Hydroxyl Radical with 1,1-Dibromoethane and 1,2-Dibromoethane Studied by Using Semi-Classical Transition State Theory

The hydrogen abstraction reaction by OH radical from CH2BrCH2Br (R1) and CH₃CHBr2 (R2) is investigated theoretically by semi-classical transition state theory. The stationary points for both reactions are located by using ωB97X-D and KMLYP density functional methods along with cc-pVTZ basis. Single-point energy calculations are performed at the QCISD(T) and CCSD(T) levels of theory with differe...

متن کامل

Nonextensive relativistic nuclear and subnuclear equation of state

Following the basic prescriptions of the Tsallis’ nonextensive relativistic thermodynamics, we investigate the relevance of nonextensive statistical effects on the relativistic nuclear and subnuclear equation of state. In this framework, we study the first order phase transition from hadronic to quark-gluon plasma phase by requiring the Gibbs conditions on the global conservation of the electri...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Journal of computational chemistry

دوره 31 3  شماره 

صفحات  -

تاریخ انتشار 2010