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## Nonequilibrium statistical theory and ab anitio approach on model electron-ionic systems

### Andrij Vasylenko

#### Abstract

Nonequilibrium processes that determine properties of the many-electrons nanoscale structures are the subject for the topical academic researches and for active implementation into technologies. Understanding of nonequilibrium processes such as adsorption, diffusion, catalytic processes, and pecularities of transport processes is essential for development of catalytic technologies, construction of superlattices, self-organizing clasters, nanostructure-based devices etc. Most of the existent theories for many-electrons systems consider nonequilibrium processes within approximation of homogeneous electron gas. Many of the theoretical approaches approximate the behaviour of the systems with linear electrochemical potential that prohibit description of strong nonequilibrium states. This doctoral thesis addresses the mentioned problems of modern nonequilibrium statistical theory of inhomogenious many-electrons and ionic structures. The stressed point of investigation is to develop an approach that allows for description of weak and strong nonequilibrium states, takes into account inhomogeneity of electron subsystem as well as discretness of ionic one, considers non-linearity of chemical potential and explicitely includes electro-magnetic interactions. In great part the conducted investigations concern the method of construction of the generalized transport equations that take into account the essential nonequilibrium processes: adsorption, desorption, electron diffusion, viscous fluxes, ionization and polarization of ions. Some researches of the considered systems are supported with the numerical calculations performed by means of the first-principles density functional theory (DFT)-based computational techniques. The work is presented with three sections. First section addresses the nonequilibrium statistical theory of inhomogeneous electron gas within jellium'' model. By means of the Zubarev nonequilibrium statistical operator (NSO) a chain of equations for the Green functions is derived. Generalized transport equations for electron-diffusion, viscous-elastic and viscous-heat approximations are obtained for model of semi-infinite metal. The results of the investigations demonstrate that NSO approach within viscous-heat approximation for inhomogeneous electron gas generalizes the approach of time-dependent current density theory (TDCDT). The results of the first section are published in four articles. In the second section the NSO method is used for description of molecular hydrodynamics of ionic melts, while taking into account polarization. The applied theory of perturbation with respect to correlations yields the spectrum of collective excitations of many-particles ionic systems. The obtained analytical results are in a qualitative agreement with the results of the generalized collective modes approach based on ab initio (considering the polarization effects) and the rigid-ion molecular dynamics simulations. The results are presented in one article. The third section demontrates the nonequilibrium statistical approach applied to adsorption processes on many-electrons nanostructure. The derived set of equations desribes processes of adsorption, desorption, ionization, polarization of gas atoms in the electro-magnetic field of carbon nanotubes. The calculations with use of density functional theory provide the values for adsorption energies of He, NO, while taking into account vacation effects; the most energetically preferable functionalization path is drown on the basis of chemisorption energies of COH, COOH groups calculated for various diameters and chiralities of carbon nanotubes. The results are published in two articles.
Record ID
Diploma type
Doctor of Philosophy
Author
Andrij Vasylenko Andrij Vasylenko,, Undefined Affiliation
Title in Polish
Nierównowagowa statystyczna teoria i technika ab initio dla modelowych układów elektronowo-jonowych
Title in English
Nonequilibrium statistical theory and ab anitio approach on model electron-ionic systems
Language
(en) English
Certifying Unit
Faculty of Physics (SNŚ/WyF/FoP)
Discipline
physics / (physical sciences domain) / (physical sciences)
Scientific discipline (2.0)
6.6 physical sciences
Status
Finished
Defense Date
19-06-2015
Title date
19-06-2015
Supervisor
URL
http://hdl.handle.net/10593/13314 Opening in a new tab
Keywords in English
nonequilibrium statistical operator, ab initio technique, transport processes, model electron-ionic nanostructures
Abstract in English
Nonequilibrium processes that determine properties of the many-electrons nanoscale structures are the subject for the topical academic researches and for active implementation into technologies. Understanding of nonequilibrium processes such as adsorption, diffusion, catalytic processes, and pecularities of transport processes is essential for development of catalytic technologies, construction of superlattices, self-organizing clasters, nanostructure-based devices etc. Most of the existent theories for many-electrons systems consider nonequilibrium processes within approximation of homogeneous electron gas. Many of the theoretical approaches approximate the behaviour of the systems with linear electrochemical potential that prohibit description of strong nonequilibrium states. This doctoral thesis addresses the mentioned problems of modern nonequilibrium statistical theory of inhomogenious many-electrons and ionic structures. The stressed point of investigation is to develop an approach that allows for description of weak and strong nonequilibrium states, takes into account inhomogeneity of electron subsystem as well as discretness of ionic one, considers non-linearity of chemical potential and explicitely includes electro-magnetic interactions. In great part the conducted investigations concern the method of construction of the generalized transport equations that take into account the essential nonequilibrium processes: adsorption, desorption, electron diffusion, viscous fluxes, ionization and polarization of ions. Some researches of the considered systems are supported with the numerical calculations performed by means of the first-principles density functional theory (DFT)-based computational techniques. The work is presented with three sections. First section addresses the nonequilibrium statistical theory of inhomogeneous electron gas within jellium'' model. By means of the Zubarev nonequilibrium statistical operator (NSO) a chain of equations for the Green functions is derived. Generalized transport equations for electron-diffusion, viscous-elastic and viscous-heat approximations are obtained for model of semi-infinite metal. The results of the investigations demonstrate that NSO approach within viscous-heat approximation for inhomogeneous electron gas generalizes the approach of time-dependent current density theory (TDCDT). The results of the first section are published in four articles. In the second section the NSO method is used for description of molecular hydrodynamics of ionic melts, while taking into account polarization. The applied theory of perturbation with respect to correlations yields the spectrum of collective excitations of many-particles ionic systems. The obtained analytical results are in a qualitative agreement with the results of the generalized collective modes approach based on ab initio (considering the polarization effects) and the rigid-ion molecular dynamics simulations. The results are presented in one article. The third section demontrates the nonequilibrium statistical approach applied to adsorption processes on many-electrons nanostructure. The derived set of equations desribes processes of adsorption, desorption, ionization, polarization of gas atoms in the electro-magnetic field of carbon nanotubes. The calculations with use of density functional theory provide the values for adsorption energies of He, NO, while taking into account vacation effects; the most energetically preferable functionalization path is drown on the basis of chemisorption energies of COH, COOH groups calculated for various diameters and chiralities of carbon nanotubes. The results are published in two articles.

Uniform Resource Identifier
urn:amu-prod:UAM0dbbc73760484278a42cb41897bade0f