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Introduction

(Problem statement)

Science main objective... sostoyoit in search of rules, zakonomernoyostej, the general laws, great zakoyonov to which the nature submits.

L.D.Landau, A.I.Kitaigorodsky. Physics for all.

Molecules

By present time, it agree «Chemical Abstracts Service press release 2010», the quantity of known molecules and substances exceeds 40 million, however eksperimenyotalnaja the base of thermodynamic properties totals no more than ten thousand sizes, thus the basic part is made by enthalpies of formation Δ - ∣H °. On radicals (R *) sootvetyostvujushchih essentially it is less than data, but even the recommended values for R*име­ют significant errors, for example, for ΔjH°до 8 - 12 kdzh/MOLE. It speaks high reactivity of radicals owing to what it is experimental ustayonovit their characteristics, as a rule, extremely inconveniently, and is frequent and it is impossible. The specified contradiction between quantity of known connections and quantity otnoyosimyh it of properties represents a vital issue, braking development of molecular physics, chemistry, engineering chemistry, a science about materials and pharmacy.

Last decade, in connection with computer facilities development, the most perspective direction of search of characteristics of connections become neempiricheyoskie kvantovohimicheskie calculations. They play a role not simply auxiliary means for an explanation of physical and chemical laws, but are one of osnovyonyh, and in some cases and the unique tool. Development of numerical methods, proyogress in electronics and the physicist have allowed to approach accuracy of predicted properties of moderately complicated molecules to accuracy of experiment.

Designing of substances with the set properties is independent and priority partition of a science. Reliable forecasting of properties demands strict teoyoreticheskih bases. Search perspek-tivnyh substances goes in different directions, but often becomes complicated in the sizes of connections. In such cases modelling of properties is made within the limits of phenomenological approaches, among them the most known are koliyochestvennye correlations "structure-property" (QSPR).zdes wide attraction of physics and theoretical chemistry allows to position and explain the found laws, and
Also, leaning against the quantum mechanics to develop and prove more strict kolicheyostvennye parities.

Optimisation of chemical processes and search of new effective technologies treyobujut the detailed and exact information on properties of substances - geometrical and elektronyonom a structure, power and thermodynamical co-ordinates (the vibration spectrum, internal rotation barriers, entropy, enthalpy, a free energy and heat capacity), and not only at 298 To, but also in wide temperature range and pressure. Starting with ukayozannyh the requirements, the necessary information on properties can be in full received on the basis of a combination of the effective settlement techniques using reyopernye data. In connection with the aforesaid, working out of reliable models and methods proyognozirovanija characteristics of connections, their realisation in program complexes, definition of reliable values of properties yet not studied substances are aktualyonymi problems of scientific search.

The purpose of the made work is

- To position, proceeding from postulates and theorems of quantum mechanics, quantitative koryoreljatsii «an electronic structure-partial property» with a substantiation fragmentayotsii connections and a kind of descriptors.

- To develop on the basis of positions of quantum mechanics and the statistical physics moyodel forecasting of authentic values of thermodynamic properties mnogoyoatomnyh connections in angarmonicheskom approach and in a wide temperature range;

In the dissertation following problems have been supplied and solved:

1. To choose optimum kvantovohimichesky a set "method/basis" on the basis of comparison of experimental and settlement parametres of reference-point connections so that to provide the best parity "accuracy/resursoemkost";

2. To calculate in angarmonicheskom vibration frequency approach in alkanes, nityoroalkanah, alkilnyh and nitroalkilnyh radicals and to find values of oscillatory contributions to thermodynamic properties in angarmonicheskom approach for the chosen substances. Methods of mathematical statistics (correlation and regressionnoe ischisyolenie) to make consideration of distribution experimental and theoretical garmoyonicheskih oscillatory frequencies;

3. To find the decision torsionnogo equations SHredingera with periodic potential of a general view in basis of plane waves. To define potential V (φ) and structural F (φ) functions of internal rotations in alkanes, nitroalkanes, alkilnyh and nitroalkilnyh radicals and to reveal laws in V (φ) and F (φ) at representation by their numbers of the Fourier.
To enter and prove criteria of shipping of parametres of internal rotation (bareyorov conformational transformations and decomposition values V (φ)).ishodja from poluyochennyh parities for V (φ), F (φ) and decisions of equation SHredingera to calculate the contribution of internal rotation to thermodynamic properties by means of summation of the found levels of energy. To study the gosh-effect phenomena (gauche-effect) and «vzaimodejyostvija tops»;

4. To find thermodynamic properties of n-nitroalkanes, n-alkilnyh and n - nitroalkilnyh radicals (standard enthalpy i a free energy δ,

S0

Entropy, heat capacity Cp, temperature shift of enthalpy Ht-H0i free eneryogii Gt-G0, and also enthalpies of opening of bond D (C-H) in a temperature band 298-1500 within the limits of developed angarmonicheskoj models;

5. To study distribution of electronic density of reference-point connections (alkanes, nitroalkanes, alkilnyh and nitroalkilnyh radicals). To characterise funktsionalyonye groups in these molecules in integrated electronic parametres in frameworks «kvanyotovoj theories of atoms in a molecule» (QTAIM), to define for them the most informative descriptors "structure" and to enter criteria of "shipping". Qualitatively and kolicheyostvenno to study interaction of nuclear groups - range of distribution and degree of decay of inductive effects. On the basis of it to prove a fragmentation modeliyoruemyh the connections, allowing to predict properties with the least error within the limits of the additive models;

6. To characterise influence of not coupled electron on distribution of electronic density of molecular fragments. To carry free valency physical (elekyotronnye) properties;

7. To analyse phenomenological additive models of calculation termodinamiyocheskih properties from the point of view of quantum mechanics and the statistical physics. To establish the occurrence reasons in them of methodical errors and to offer exception procedures (or minimisation) these errors;

8. To create the computer programs realising offered model.

Management of chemical processes and understanding of mechanisms of reactions predpolayogajut knowledge of thermodynamic properties in wide temperature range. However their experimental definition for many substances is complicated, therefore in chemistry more and more the attention is given to physical and mathematical models which expand vozyomozhnosti experiment. Calculations play the important role in definition of a structure of molecules, a finding of local and global minima, transient states, power
Barriers, vibration spectrums and thermodynamic properties. The basic improvement of accuracy of calculations goes in a direction of increase in number of basic functions and more polyonogo the account of interelectronic correlation. But such development while is limited by moderately difficult connections. Modelling of the big polyatomic molecules demands druyogogo the approach - designing of connections from separate fragments with transferring of the properties connected with these fragments. Therefore it is necessary to search and postulate perenoyosimye combinations of atoms (with electronic density falling into with it) in those veshcheyostvah where there is a possibility to carry out calculation with high accuracy, and to be able to make of them more difficult connections. Thus it is important to know correct conformstion fragyomentov as at chain escalating it is possible to receive connection, it is significant otyolichajushcheesja on a structure from the assumed.

The theoretical importance of work is defined all-round kvantovomehaniyocheskim by the analysis with instructions of borders of applicability of widely used theoretical models of definition of thermodynamic properties; the found laws in electronic, structural, power, spectroscopic, thermodynamic payorametrah and an establishment of interrelations between them; received analytical vyrayozheniem for matrix elements gamiltoniana and own numbers (full energy) torsionnogo equations SHredingera; construction on this basis of more exact forecasting model of thermodynamic properties, and also possibility further sovershenyostvovanija models within the limits of the quantum mechanics and the statistical physics.

The role of free radicals in the big number of the processes having a wide range of application is positioned exclusively important, and frequently defining. TrudnoYOsti researches of a structure and properties of the free radicals, connected with their reactivity and small time of a life, define scarcity and discrepancy sootyovetstvujushchih literary data. Developed and approved in the dissertation moyodel allows to carry out with high accuracy mass calculations of properties of radicals and molecules in wide temperature range, and for the big polyatomic connections schemas in frameworks makroinkrementirovannija are offered and the additive approach, pozvoljayojushchie to get enthalpy of education with the least methodical error.

The practical importance of the yielded work in the field of molecular physics, hiyomii and engineering chemistry is defined resulted in it structural, spektroskoyopicheskie, by power and thermodynamic properties of nitroalkanes, hydrocarbonaceous and nitroalkilnyh radicals: parametres of an electronic and geometrical structure, poyotentsialnye functions of internal rotation and dependence of a structural constant on two-sided angle, oscillatory (harmonious and angarmonicheskie) and torsionnye spekyo
try, thermodynamic functions and enthalpies of bond breaking, and also realisation of the found quantitative parities in original software products.

To studying of a structure and physical and chemical parametres of n-alkanes it is devoted bolyoshoe quantity of works. They well also are full characterised by the thermodynamic properties, therefore the yielded connections are often considered as modelling at proyoverke various hypotheses. Interest to studying of a structure and properties of nitro compounds opreyodeljaetsja their wide application as explosives and components raketyonyh topliv. However their thermodynamic properties at various temperatures vychisyoleny in harmonious approach (and with a significant error at high temepera - rounds) only for the limited quantity of substances (Stall D, Vestram E, Zinke G, Hiyomichesky thermodynamics of organic compounds. M: the World, 1971. - 806 with.) . SushchestvujuYOshchy fund of data on structural and power, spectral and termodinamicheyoskim properties of hydrocarbonaceous radicals can characterise as very poor and inconsistent. In the literature fragmentary data about frequencies kolebayony (one or several values of frequencies) only for 30 hydrocarbonaceous radicals with chisyolom atoms of carbon from 2 to 7 (according to NIST, http://are presented webbook.nist.gov/chemistry/form - ser.html), thus by full vibration spectrums is characterised 6 of them. EdinYOstvennye regular researches of vibration spectrums of a narrow class alkilyonyh radicals on the basis of experiment (IK in argonovyh matrixes) and kvantovoyohimicheskih calculations with basis use 6-31g in harmonious approach have been made in the eighties (Pacansky J. et al.) And now these results demand peyoresmotra from positions of specification of a method and the account angarmonizmov. Calculations of potential functions and torsionnyh levels kvantovohimicheskimi for polyatomic radicals were not made earlier by methods of a high level. By sizes of standard enthalpies obyorazovanija it is at present characterised about 200 hydrocarbonaceous and two nit - roalkilnyh a radical. In reference books (Orlov J.D., Lebedev J.A., Sajfullin I.S., Thermochemistry of organic free radicals. M: the Science, 2001. - 306 with. And Luo J. - R., Comprehensive handbook of chemical bond energies. N.-Y.: Crc Press, Vosa Raton, 2007. 1657 p.) the significant part of the resulted data on their enthalpies of formation is noted by criterion "pre-award". In database NIST

(http://webbook.nist.gov/chemistry/form-ser.html) there are values of enthalpies obrazoyovanija all for 14 hydrocarbonaceous radicals. Other thermodynamic properties (enyotropija, heat capacity, a free energy of Gibbs, entalpijnyj shift) in wide interyovale temperatures are presented in the literature not quite reliable values for less than 10 most simple connections, thus IUPAC are recommended values only
For two hydrocarbonaceous radicals - methyl and benzil (Ruscic B., Boggs J.E., Burcat A.G., Csaszar A.G., Demaison J., Janousek R., Martin J.M.L., Morton M.L., Rossi M.J., Stanton J.F., Szalai P.J., Westmorilend P.R., Zabel F. Berces T. / IUPAC critical evaluation of thermochemical properties of selected radicals//J. Phys. Chem. Ref. Data. 2005 V. 34, № 2, p. 573-656). Researches of an electronic structure of radicals in frameworks "the quantum theory of atoms in a molecule" QTAIMкрайне a little: 7 publications on the yielded theme are known only, 4 from which are prepared at personal participation of the author. Thus, for the first time found in work structural, spectroscopic, electronic, power and termodinamiyocheskie properties of n-nitroalkanes, n-alkilnyh and n-nitroalkilnyh radicals (C*H2 (CH2) nCH3, CH3 (CH2) nNO2и C*H2 (CH2) nNO2, at n ≤ 8), are represented znachitelyonuju scientific novelty.

Possibility of reduction of a settlement error of property occurs then, koyogda there is an understanding of "the internal device» used models, and them postroeyonie is carried out on the basis of strict physical laws. The model of division of movements (forward, rotary, oscillatory, internal rotation and electronic) result ins additivities of full energy of a molecule and additivity of thermodynamic properties of substances - to their representation in the form of the sum of contributions - forward, vrashchayotelnogo, oscillatory, electronic, internal rotation. Now rasyochet first two summands does not meet any difficulties, however correct opredeyolenie components of electronic and oscillatory movements, and also internal vrayoshchenija demands essential efforts, especially for radicals and intermediatov.

The spectral analysis is one of the most powerful tools in fizicheyoskojhimii. The knowledge of spectral characteristics allows to make identification of connections, to study a course of chemical reactions. Values of vibration frequencies are used as at definition of fundamental transferrings and overtones and their reference under forms of fluctuations at decoding of experimental spectrums, and at definition termoyodinamicheskih properties. However full and consistent sets of experimental frequencies with references under the form and symmetry are known for the limited number dostatochyono simple molecules and very little for radicals. In similar cases, along with ekspeyorimentom, the big role play kvantovomehanicheskie calculations.

Estimation of thermodynamic properties of substances routinely make to models «a rigid duplicator - a harmonious oscillator» (ЖРГО1). In approach ZHRGO vibrational levels are located in parabolic potential trough ekvidistantno and at summiyorovanii it is supposed, that their number is infinite. The parities used for opreyodelenija of thermodynamic properties at standard temperature, yield udovletvoriyo
telnoe the consent with experiment (basically for enthalpy) if is not present essentially an - harmonious fluctuations, and deviations of the found frequencies from experimental sizes makes less than 25 sm-1. However a significant part of theoretical spectrums, poluchenyonyh in harmonious approach, have an error to 100 sm-1i more, what not pozyovoljaet to use them for achievement of "chemical accuracy». In such cases prihoyoditsja or to pass to angarmonicheskoj models, or to level the big difference between theoretical and experimental values scaling procedure. Scaling allows to receive the consent with experiment for the oscillatory contribution, but only in one point of a temperature band (it is routine 298).

In the dissertation methods of mathematical statistics (correlation and regressiyoonnyj the analysis) analyse procedure of scaling harmonious kolebayotelnyh frequencies. It has been proved, that dependence ω3κcn = f (ωpac4) between settlement and eksyoperimentalnymi frequencies is linear and the scaling equation should contain a free member, thus for all compared spectrums it is significantly distinct from zero.

In the literature there are numerous examples of calculations of spectrums by means of different methods and bases though applicability of the chosen combination a method/basis obosyonovyvaetsja it is rare. In work comparison experimental and theoretical - calculated in various combinations a method/basis - harmonious agarm and angarmoniyocheskih tangarm oscillatory frequencies on an example of n-alkanes is made. Basically, sets MP2∕6-311 ++ G (3df, 3pd), B3LYP∕6-311 ++ G (3df, 3pd) and B3LYP∕aug-cc-pvQZ were used. pokayozano, that angarmonicheskoe approach with combination B3LYP∕6-311 ++ G (3df, 3pd) pozvoyoljaet to receive uangarm with standard deviation less than 25 sm-1. Therefore garmoyonicheskie frequencies of the studied n-alkanes, N-NITROALKANES, n-alkilnyh and n - nitroalkilnyh radicals are found by methods B3LYP∕6-311 ++ G (3df, 3pd) and B3LYP∕aug-cc - pvQZ. Angarmonichesky frequencies are calculated by means of B3LYP/6-311 ++ G (3df, 3pd) in koyolebatelnoj theories of perturbation of the second order with kvartichnym a force field (VT2 QFF), and tangarm for initial homologues also a method oscillatory samosoglasovanyonogo fields (VSCF).

Calculations of thermodynamic properties of polyatomic connections in model ZHRGO at the temperatures exceeding 298 To, routinely result ins to a significant error, here again it is required to use more exact parities, i.e. to pass to angarmonicheyoskoj models, as it is made in the yielded work. In the dissertation, leaning against methods statiyosticheskoj physicists, the model «a rigid duplicator-angarmonichesky an oscillator» is developed
(ZHRAO) where oscillatory contributions to thermodynamic properties are calculated by direct summation on angarmonichnym oscillatory and torsionnym to levels.

Studying of the phenomenon of internal rotation is one of the most difficult and resuryosoemkih quantum chemistry problems. Complexity and IK torsionnyh eksyoperimentalnyh spectrums sharply increases in interpretation MV with increase in length of a molecular chain and for the connections containing 5 and more tops, reference of lines of torsional vibrations becomes ambiguous. The decision torsionnogo equations SHredingera yields position of energy levels and value of frequencies of transferrings in long-wavelength part IK spekyotra. Here calculation supplements experiment as the calculated frequencies allow obosyonovat reference of experimental frequencies and to carry them on konformeram. Knowledge parayometrov internal rotation in molecules very important for development of methods molekuljaryonogo modelling. Computer designing of the big nonrigid molecules in silico bases on libraries of structural characteristics and potential functions V (φ). However direct definition V (φ) at present is limited moderately slozhnyyomi by molecules.

Definition of the contribution of internal rotation in thermodynamic properties in ramyokah the developed model demands the pre-award decision torsionnogo equation SHredingera. In the presented work torsionnogo equations SHredingera with periodic potential of a general view the decision has been found in basis of plane waves when also potential function V (φ), and structural function F (φ) Fouriers both on sine and on kosinusam are presented in a kind razlozheyonija abreast. I.e. the decision is received as for simmetrichyonyh functions V (φ) = V (-φ) and F (φ) = F (-φ), asymmetric functions V (φ) =-V (-φ) and F (φ) = - F (-φ), and for general view functions. Research of all has been carried out the dissertation internal rotation in CH3 (CH2) nCH3, CeH2 (CH2) nCH3, CH3 (CH2) nNO2и CeH2 (CH2) nNO2, at n ≤ 8, and 224 potential functions V (φ) are defined. For nitroalkanes and nit - roalkilnyh radicals dependences of structural constants F (φ) from two-cut angle (91 function) are received. All calculations are made by method B3LYP∕6-311 ++ G (3df, 3pd), and for initial homologues also MP2/6-311 ++ G (3df, 3pd). The gosh-effect phenomenon (equality full energy (enthalpies of formation) konformerov has been studied at a trance, gosh + and gosh - group NO2 position) in N-NITROALKANES CH3 (CH2) nNO2и n-nitroalkilnyh radiyokalah CeH2 (CH2) nNO2, at 3 ≤ n ≤ 8. In initial homologues the phenomenon of "interaction of tops» («interaction of movements») when at top rotation otyonositelno a skeleton it is observed the co-ordinated movements of atoms in nuclear groupings making them has been considered. In the dissertation the problem of definition of levels of energy of torsional vibrations in most general case of asymmetric internal rotation has been solved
Also the complete set of the programs is developed, allowing to calculate the yielded contribution in termodinamiyocheskie properties within the limits of offered model.

Empirical modelling of structure and properties leans against the quantitative correlations connected with shipping of parametres. Therefore it is important to search perenosiyomye for combinations of atoms in those molecules where there is a possibility to carry out calculation with vysoyokoj accuracy, to define their partial properties and to find similar structures in the big molecules. Search of quantitative correlations "structure-property" for vnutyorennego rotations yields the best results at research of homologous series. For intermediatov, owing to small time of a life, literary data on studying of these degrees of freedom are absent, and by present time internal rotation in rayodikalah practically is not investigated. In work, proceeding from the received set V (φ), position in a molecular chain and a kind of transferable fragments of n-alkanes, n - nitroalkanes, n-alkilnyh and n-nitroalkilnyh radicals is found, to which are supplied in sootyovetstvie generalised (average) transferable potential functions Rsr () and baryoery.

Now there are three ways of definition of properties of molecules and radiyokalov - experiment, the decision of equation SHredingera for all movements of the chosen elektronno-nuclear system and modelling (for example, the additive-group approach and makroinkrementirovanie). In case of the former it is not always possible, especially for trebuyoemogo a temperature band, therefore the increasing attention reverts on the second and third possibilities. But also in the second case the decision receive only at significant simplifications, and for enough big molecules correct calculation is at present impossible. In this situation unique there are the approaches developed in frameworks moyolekuljarnogo of modelling where molecules represent set of fragments, obyoladajushchih shipping together with corresponding partial shares of properties.

Now development of the additive approaches, as a rule, is carried out in a direction of their trivial expansion on new classes of connections with increase in number of parametres, for example, by introduction of new types of effective fragments (groups) and the various corrections correcting initial model. Most widely ispolzueyomye phenomenological models are based on a hypothesis that molecular parayometry and descriptors of fragments are defined or the formula, or proyostranstvennym by an arrangement of kernels, or by the molecular count (QSPR).dannoe poloyozhenie is taken over as a postulate as to deduce theoretically size of the contribution from a kind of a fragment or a relative positioning of its atoms (a descriptor "structure") nevozmozhyono. Therefore, in such models at introduction of descriptors there is a certain arbitrariness,
Result ining to that nothing guarantees correctness of total figure. The decision of a return problem at parametrization QSPRв such approach result ins casual koryoreljatsijam, well working only in borders of training set moyolekul. Presence of a significant error and misses at a yield for frameworks of training set demands transferring from empirical modelling to constructions on the basis of strict theorems and postulates.

The recent trend consists in redefinition of parametres used moyodelej and to transferring to the analysis of an electronic structure. Distribution electronic plotnoyosti allows to consider changes in characteristics of "identical" groups (formally odiyonakovyh groups) to yield quantitative measures arising at their connection «nevalentyonym to interactions» and to nonadditive additives. It is clear, that similar consideration should be made within the limits of the quantum and statistical mechanics. The quantum physics considers a molecule, as a set of definitely located kernels, pogruyozhennyh in electronic density. The theorem of the Hoenberga-game and «the holographic theorem» have put in pawn a basis of theoretical chemical modelling, and also a search basis peyorenosimyh fragments. The main consequence of theorems: all individual properties of molecules and groups making them are defined by distribution of their electronic density (p (r)). Communication of terms of the classical theory of a structure of molecules with properties electronic plotyonosti is carried out in frameworks «the quantum theory of atoms in molecules» QTAIM.Здесь the additive approaches based on shipping of properties funktsionalyonyh of groups, as consequence of shipping of electronic density of these groups are involved. Therefore osyonovnoj the emphasis in development QSPRи QSARпостепенно is displaced from modelling of a nuclear structure to modelling of distribution of electronic density.

The electronic density within the limits of QTAIMможет to be unequivocally defined and razyodelena on the "basins" concerning, as a rule, to separate kernels. These basins (vmeyoste with the kernels) are called as "effective" or "topological" atoms (Ω), and their internuclear borders coincide with surfaces of a zero stream of a vector of a gradient of electronic density. For each such atom it is possible to find a charge (q (Ω)), as the sum of negative charge of its electronic basin and positive charge of a kernel, volume (V (Ω)), full energy (E (Ω)) and other characteristics. Making of atoms funktsioyonalnye and nuclear groups (R), it is possible to enter a group charge (q (R)), energy (E (R)) and volume (V (R)). The yielded quantitative measures are on the one hand a measure perenosiyomosti, and with another are connected with partial properties of groups. Modelling ramyokah consists in these in vostanovlenii pr) a new molecule from suitable fragments pR (taking into account change pR () in the field of intergroup (internuclear) borders. Action liganyo
dov (inductive effect) within the limits of QTAIMопределяется change of the charges full energy, volumes of functional groups. Additivity of electronic density privoyodit to additivity of contributions of fragments in thermodynamic properties, thus velichiyona an arising error of total property is defined by distinction in the initial and transferred electronic density.

In the dissertation the specified parametres in CH3 (CH2) nCH3, CeH2 (CH2) nCH3, CH3 (CH2) nNO2и CeH2 (CH2) nNO2 are found, at n ≤ 8, (in nitroalkanes and nitroalkilnyh radicals taking into account gosh-effect) for all fragments R.Введены of the characteristic transferable "standard", "partially transferred" (in concrete position in a molecular chain) and intolerable ("unique") groups. It is investigated interferences of groups in molecules

- Inductive and steric effects.

Reactivity of radicals, their instability, conformational and eneryogeticheskie properties are defined distribution of electronic density, and, basically, that its part that falls into to the not coupled electron. The electronic density nesparenyonogo an electron also is carried on basins of this or that atom that defines its localisation and delokalizatsiju. In work distribution electronic plotyonosti in n-alkilnyh radicals has been studied and influence of free valency on fizikoyohimicheskie properties of connections is defined.

The ways of calculation of contributions offered in the dissertation in properties in angarmonicheyoskom approach have laid down in a basis angarmonicheskoj models. The model developed in the dissertation correctly reproduces available literary data. Studied raspreyodelenija electronic density, inductive effects, communication integrated harakteriyostik distributions of electronic density with thermodynamic, structural and power properties have allowed to develop basic positions of mathematical model "structure-property" within the limits of phenomenological additive-group podyohoda on the basis of electronic characteristics of groups, to position methodical pogreshyonosti the additive approaches and to offer paths of their exception. The yielded approach otkryvayoet possibility of "designing" of connections from transferable fragments of molecules and radicals to count the contribution of these fragments to enthalpies of formation, that, in turn, allows to model molecules and radicals of more difficult (concerning considered) structures and to define their enthalpies of formation. Stated above poyolozhenija make methodology and methods of research of the yielded work.

On protection are taken out:

- Development of methods of forecasting of thermodynamic properties on the basis kvantovoyomehanicheskih representations;

- Model of calculation of thermodynamic properties of substances in a temperature band 298 - 1500 To in angarmonicheskom approach;

- angarmonicheskie spectrums for 35 molecules of homologous series CH3 (CH2) nCH3, CeH2 (CH2) nCH3, CH3 (CH2) nNO2 (with the account konformerov) and CeH2 (CH2) nNO2 (with the account konyoformerov);

- 224 potential functions of internal rotation, from them 37 potential functions of n-alkanes CH3 (CH2) nCH3,34 potential functions of rotation in n-alkilnyh radicals CeH2 (CH2) nCH3, 78 potential functions CH3 (CH2) nNO2 (with the account konformerov) and 75 potential functions CeH2 (CH2) nNO2 (with the account konformerov);

- 91 structural functions of internal rotation, from them 44 structural functions CH3 (CH2) nNO2 (with the account konformerov) and 47 structural functions CeH2 (CH2) nNO2 (with ucheyotom konformerov);

- The decision torsionnogo equations SHredingera with periodic potential of the general viyoda in plane waves;

- Thermodynamic properties (standard enthalpy of formation, a free energy of Gibbs, entropy, heat capacity, dependence of enthalpy of opening of bond D (C-H) in diapayozone 298 - 1500) the chosen reference-point molecules;

- Substantiation of a fragmentation and the additive schemas of calculation of properties of alkanes, nitroalkanes, alkilnyh and nitroalkilnyh radicals (CH3 (CH2) nCH3, CeH2 (CH2) nCH3, CH3 (CH2) nNO2 and CeH2 (CH2) nNO2) taking into account inductive effects, shipping of fragments and values of partial properties;

- Theoretical bases of construction of quantitative correlations "structure-property" with the least methodical error;

- The computer programs realising offered angarmonicheskuju model.

The dissertation material is stated in 164 publications, including 59 articles, from them in magazines from list VAK 41, 93 theses of reports on Russian and international konfeyorentsijah, and also in 9 software products on which certificates gosuyodarstvennoj registration are received.

The present work is executed on chair of the general physics Tver gosudarstvennoyogo university.

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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

More on topic Introduction:

  1. in introduction
  2. INTRODUCTION
  3. INTRODUCTION
  4. 10.1. Introduction
  5. INTRODUCTION
  6. approbation and introduction of results.
  7. Introduction
  8. Introduction
  9. INTRODUCTION
  10. INTRODUCTION
  11. Introduction