The application of numerical inversion of the laplace transform to calculate the density of molecular states

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Дәйексөз келтіру

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Аннотация

To estimate the rate constants of monomolecular reactions using quasi-equilibrium statistical theory, information on the density of discrete states of molecules is required. In the present work, a new approach to calculating the density of discrete states of stable molecules and transition complexes is proposed, which is based on the numerical inversion of the Laplace transform. To test the method, the calculations of model systems including H₂O, NH₃, CD4 and с-C₃H₆ molecules were carried out. It is shown that at energies less than 200 kcal/mol, the relative error in calculating the density of discrete states does not exceed 0.5%. The results obtained by this method can be used, for instance, to estimate the rate constants of reactions involving organic radicals formed in the troposphere and tropopause.

Толық мәтін

Рұқсат жабық

Авторлар туралы

S. Adamson

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Хат алмасуға жауапты Автор.
Email: sergey.o.adamson@gmail.com
Ресей, Moscow

D. Kharlampidi

Moscow State Pedagogical University; RUDN University

Email: sergey.o.adamson@gmail.com
Ресей, Moscow; Moscow

G. Golubkov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences; National Research Center “Kurchatov Institute”

Email: sergey.o.adamson@gmail.com
Ресей, Moscow; Moscow

Y. Dyakov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Ресей, Moscow

I. Morozov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Ресей, Moscow

O. Olkhov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Ресей, Moscow

I. Rodionov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Ресей, Moscow

I. Rodionova

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Ресей, Moscow

I. Stepanov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Ресей, Moscow

D. Shestakov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Ресей, Moscow

M. Golubkov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Ресей, Moscow

Әдебиет тізімі

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2. Fig. 1. Dependence of the root-mean-square error σ(W) for the H₂O molecule on the ratio Eₘₐₓ/Eᵤ.

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3. Fig. 2. Dependence of the lower values ​​of the function W(E ) for the H₂O molecule on the ratio Eₘₐₓ/Eᵤ: circles correspond to energy E = 5 kcal/mol; squares – E = 10 kcal/mol; diamonds – E =15 kcal/mol.

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4. Fig. 3. Dependence of the relative calculation error DW/W(E ) on the energy E for model systems: circles — H₂O molecule; squares — NH₃; diamonds — CD4; triangles — c-C₃H₆.

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