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Entropies of Condensed Phases and Complex Systems: A First Principles Approach: Springer Theses

Autor Christian Spickermann
en Limba Engleză Paperback – 27 feb 2013
Predicting thermodynamic quantities for chemically realistic systems on the basis of atomistic calculations is still, even today, a nontrivial task. Nonetheless, accurate treatment of inter-particle interactions, in terms of quantum chemical first principles methods, is a prerequisite for many applications, because of the complexity of both reactants and solvents in modern molecular sciences. Currently, a straightforward calculation of thermodynamic properties from these methods is only possible for high-temperature and low- density systems. Although the enthalpy of a system can often be predicted to a good level of precision with this ideal gas approach, calculating the entropy contribution to the free energy is problematic, especially as the density of the system increases. This thesis contains a compact and coherent introduction of basic theoretical features. The foundations are then laid for the development of approaches suitable for calculation of condensed phase entropies on the basis of well-established quantum chemical methods. The main emphasis of this work is on realistic systems in solution, which is the most important environment for chemical synthesis. The presented results demonstrate how isolated molecular concepts typically employed in modern quantum chemistry can be extended for the accurate determination of thermodynamic properties by means of scale- transferring approaches.
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Specificații

ISBN-13: 9783642266782
ISBN-10: 3642266789
Pagini: 244
Ilustrații: XVI, 225 p.
Dimensiuni: 155 x 235 x 13 mm
Greutate: 0.35 kg
Ediția:2011
Editura: Springer Berlin, Heidelberg
Colecția Springer
Seria Springer Theses

Locul publicării:Berlin, Heidelberg, Germany

Public țintă

Research

Cuprins

Introduction.- From atomistic calculations to thermodynamic quantities.- Assessment of the rigid rotor harmonic oscillator model at increased.- Densities.- Liquid phase thermodynamics from the quantum cluster equilibrium.- model.- Phase transitions.- Outlook.

Textul de pe ultima copertă

Predicting thermodynamic quantities for chemically realistic systems on the basis of atomistic calculations is still, even today, a nontrivial task. Nonetheless, accurate treatment of inter-particle interactions, in terms of quantum chemical first principles methods, is a prerequisite for many applications, because of the complexity of both reactants and solvents in modern molecular sciences. Currently, a straightforward calculation of thermodynamic properties from these methods is only possible for high-temperature and low- density systems. Although the enthalpy of a system can often be predicted to a good level of precision with this ideal gas approach, calculating the entropy contribution to the free energy is problematic, especially as the density of the system increases. This thesis contains a compact and coherent introduction of basic theoretical features. The foundations are then laid for the development of approaches suitable for calculation of condensed phase entropies on the basis of well-established quantum chemical methods. The main emphasis of this work is on realistic systems in solution, which is the most important environment for chemical synthesis. The presented results demonstrate how isolated molecular concepts typically employed in modern quantum chemistry can be extended for the accurate determination of thermodynamic properties by means of scale- transferring approaches.

Caracteristici

Nominated by Wilhelm-Ostwald Institute of Physical and Theoretical Chemistry Leipzig, Germany, for a Springer Theses Prize Demonstrates how the systematic improvement of calculated thermodynamics is possible using highly accurate quantum chemical data and applying models and methods Increases our understanding of the nature of condensed phase thermodynamics Includes supplementary material: sn.pub/extras