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philosophy of construction of phenomenological models and the thermodynamic databases connected with them

The significant part of modern phenomenological models is created on the basis of classical theories of a structure, and proceeding from classical positions. In this connection their accuracy is low, they do not possess completeness of the description, and there are only two paths of improvement prognosticheskoj possibilities of similar theoretical constructions:

- Indemnification of errors by introduction of additional empirical parities («vysokourovnevyh corrections HLCyy,« not valent interactions "," steric interactions », scaling multipliers,« pressure of cycles »etc.). But such procedures operate only on that set on which it has been made payorametrizatsija and do not possess flexibility.

- The exception of models of a regular error, as is offered in chapter 6.

Phenomenological models together with thermodynamic intellectual databases should consist of training set recommended eksperiyomentalnyh values, test set and a superstructure, allowing to generate new unknown connection from fragments. The detailed consideration made in the yielded Chapter on a basis kvantovomehanicheskogo of the analysis, has shown, that definition teryomodinamicheskih properties with the least error (in a limit with «chemical tochnoyostju») is possible within the limits of the constructions based on following postulates:

- Exception of training set of small molecules (with number of atoms less than 10);

- Exception of making external degrees of freedom of thermodynamic properties of molecules of training set before model parametrization;

- Descriptors "structure" of quantitative correlations "structure-property" (QSPR) should be electronic, instead of nuclear characteristics, in quality kotoyoryh the charge, volume or the full energy, found in frameworks QTAIM can be offered;

- The size characterising a descriptor "property", should be supplied in funkyotsionalnuju or correlation dependence on its electronic structure;

- The way of splitting of a studied molecule on fragments should consider features of distribution of electronic density;

- Molecules of training set should be broken into such fragments that soyochlenenie occurred on groups with equal or close elektrootritsatelnostjayomi and to avoid part inclusion pR () one fragment in other fragment;

- Collective effects should be deduced from parametres intermolecular vzaimoyodejstvija, believing as those characteristics p (r) intermolecular communications and funktsionaly pR (r) groups connected by them;

- The superstructure should include the splitting module p (r) a studied molecule and molecules of the training set, dynamically creating in the course of calculation new base R, pR () and F [p (], proceeding from the stated above and set criteria stated above by the user or from prospective properties of a modelled molecule;

- The module of calculation of properties should contain procedures QSPR connecting partsiyoalnye properties P (R), absent in a database, from them pR ().

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A source: Turovtsev Vladimir Vladimirovich. Creation and application of a quantum mechanical model for calculating the thermodynamic properties of substances in a wide range of temperatures. Thesis for the degree of doctor of physico-mathematical sciences. Tver - 2014. 2014

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