CC BY
13
UDC 547.64:544.183.26
V. A. Babkin, V. Yu. Dmitriev, D. S. Andreev, A. A. Pristanskov, М. N. Gulyukin, А. S. Belousov, A. N. Ignatov, D. A. Hramogin, V. T. Fomichev, Kh. S. Abzaldinov, G. E. Zaikov
CONFORMER OF OPTICAL SYSTEM SILICON DIOXID - 3Na2O
Keywords: conformer, optical molecular system, quantum-chemical calculation, silica dioxide-sodium oxide (1:3), PM3 method, acid
force, universal indicator of acidity.
The quantum chemical calculations of system SiNaeOjH4 in the framework of the molecular model have been executed by PM3 method for the first time. The most energetically favorable configuration of the studied system (conformer) has been selected. Theoretically estimated acid force of the conformer (pKa) is 13. This compound belongs to a class of weak H-acid (9 < рКа < 14).
Ключевые слова: конформер, оптические молекулярные системы, квантово-химический расчет, диоксид кремния - оксид натрия (1:3), метод PM3, кислотная сила, универсальный показатель кислотности.
Впервые проведены квантово-химические расчеты системы SiNaeOjH4 в рамках молекулярной модели методом PM3. Выбрана наиболее энергетически выгодная конфигурация исследуемой системы (конформер). Оцененная теоретически кислотная сила конформера (pKa) равна 13. Это соединение относится к классу слабой H-кислоты (9 <рКа <14).
Introduction
The calculations of the system SiO2 - Na2O by PM3 method are very necessary for performing dependencies of the optical parameters (refractive index, viscosity, etc.) of this system with the different ratio of stoichiometric coefficients (1:1, 1:2, 1:3, 1:4, 1:5, etc.) on the quantum parameters (the total energy (E0), the maximum charge on the hydrogen atom (qH+max), the energy of the highest occupied molecular orbital (EHOMO), the lower energy unoccupied molecular orbital (Elumo), the energy zone (gap) (Ez), the dipole moment (D), and others), received on the basis of these models at the nanoscale by classical methods of quantum chemistry. PM3 method is specifically parameterized for calculating of hypervalent compounds. This method reproduces well the geometry of the molecules, hydrogen bonds and heat of formation [1]. The quantum-chemical calculation of the optical system SiO2 - Na2O with 1:1 stoichiometric ratio by PM3 method was implemented in [2]. The aim of the investigation is to carry out the same calculation of the same system with 1:3 stoichiometric ratio and found the geometric and electronic structure of the most energetically favorable conformer.
Experimental
The first quantum chemical calculations of optical systems have been carried out in [7-14] by method MNDO within the polymer molecular model by D. I. Mendeleev. The quantum chemical method PM3 is necessary to use for tetrahedral models of molecular type [15-20]. It is programmed for calculating the hypervalent compounds. These compounds are hypervalent. Method reproduces the geometry of molecules, hydrogen bond and formation heat [3].
The PM3 method has been selected for quantum chemical calculation of various configurations and isomers of SiO2 - 3Na20 system. The method is based on PC GAMESS [3]. The calculation of the studied systems was carried out in the framework of the molecular model with geometry optimization of all
parameters to standard gradient method, built in Firefly program [4]. Method is partially based on GAMESS (US) source code [5] in the approximation of isolated molecules in the gaseous phase and the ground state. The total charge for all models is always 0. The multiplicity M = 1. All models have paired electrons. The total spin S = 0. M=2S+1=1. The models of the studied system were presented in the framework of the molecular cluster SiNa6O7H4. The known program MacMolPlt was used for a visual representation of molecules models [4]. A theoretical estimate of the acid force of the investigated SiO2 - 3Na20 molecular systems was performed according to the formula pKa=42.936-165.11qmaxH+ (where, qmaxH+ - the maximum charge on the hydrogen atom, pKa - the universal indicator of acidity). The formula is obtained by us according to [2, 7], but for the PM3 method. This formula is very successfully used to assess of various indenes acid force [20-22]. The authors obtained a good agreement with published data for these compounds [23].
Results and Discussion
We studied 18478 various configurations and isomers of the system. The quantum chemical parameters of the 9 most energetically favorable one are calculated by PM3 method (Fig. 1, Table 1). Model (conformer) №10 has a maximum total energy (E0) and is shown in Figure 2.
The values of pKa for the most energetically favorable conformations have been determined by the formula pKa=42.936-165.11qmaxH+ [6]. pKa = 13. Values EHOMO and ELUM0 (Table 1), depending on the macro parameters (refractive index, viscosity, etc.), are interesting for studying.
The quantum chemical calculation of different configurations and isomers of SiO2 - 3Na20 system by PM3 method within a SiNa6O7H4 molecular cluster was performed for the first time. We reviewed 18478 of various conformations and isomers. Conformer - isomer with a maximum total energy was found. Its basic quantum chemical parameters were obtained: the total energy (E0, kJ/mol), maximum charge on the hydrogen
h+
atom (q max), universal indicator of acidity (pKa), the energy of the highest occupied molecular orbital (EHOMO, kJ/mol), the energy of the lowest unoccupied molecular orbital (ELUM0, kJ/mol), the energy area (gap) (E^, kJ/mol), the dipole moment (D, dB). 10 of the most energetically favorable configurations and isomers of system SiNa6O7H4 were determined. Their acid force was theoretically evaluated. pKa = 13. These conformers belong to the class of weak H-acids.
Fig. 1 - Various isomers configuration of SiNa6O7H4 system
Table 1 - The quantum chemical parameters of the 9 most energetically favorable isomers and conformer
№ о S M о ш га е + i ст pKa Еномо, kJ/mol Elumo, kJ/mol , "о kl fi E /J k 9 о"
1. -216648 0.17 15 -704 203 907 3.59
2. -216641 0.17 15 -682 206 888 9.14
3. -216639 0.17 15 -732 180 912 5.37
4. -216638 0.16 17 -702 190 892 4.87
5. -216637 0.17 15 -733 182 915 7.53
6. -216634 0.16 17 -733 182 915 8.19
7. -216632 0.17 15 -725 204 929 2.96
8. -216625 0.18 13 -719 168 887 2.14
9. -216624 0.18 13 -719 169 888 8.39
10* -216651 0.18 13 -700 200 900 3.76
* - conformer
Fig. 2 - The geometric and electronic structure of the molecule conformers of SiNa6O7H4 optic system (E0=-216651 kJ/mol)
Conclusions
The total energy (E0. kJ/mol), the maximum charge on the hydrogen atom (qH+max), the universal indicator of acidity (pKa), the energy of the highest occupied molecular orbital (EHOMO, kJ/mol), the energy of the lowest unoccupied molecular orbital (ELUM0, kJ/mol), the energy area (gap) (E^, kJ/mol) and dipole moment (D, dB) for the most energetically favorable configurations and isomers of SiO2 - 3Na20 system have been obtained.
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© V. A. Babkin - Doctor of Chemistry, Full Professor, Academician of Russian Academy of Nature, Academician of International academy "Contenant", Volgograd State Technical University, Sebrykov's Branch, E-mail: [email protected], V. Yu. Dmitriev -Post-Graduate Student of Volgograd State Technical University, Sebrykov's Branch, D. S. Andreev - Lecturer of Volgograd State Technical University, E-mail: [email protected], A. A. Pristanskov - Lecturer, Post-Graduate Student of Volgograd State Technical University, Sebrykov's Branch, М. N. Gulyukin - Lytkarino Optical Glass Factory, A. S. Belousov - Lytkarino Optical Glass Factory, A. N. Ignatov - Lytkarino Optical Glass Factory, D. A. Hramogin - Lytkarino Optical Glass Factory, V. T. Fomichev — Doctor of Engineering, Full Professor of Applied Chemistry Department, Volgograd State Architecture Building University, [email protected], Kh. S. Abzaldinov - Ph.D., Associate Professor of Plastics Technologies Department, KNRTU, G. E. Zaikov - Doctor of Chemistry, Full Professor of Plastics Technologies Department, KNRTU.
© В. А. Бабкин — д-р хим. наук, проф., академик РАЕ, академик Международной академии «Контенант», e-mail: [email protected], В. Ю. Дмитриев - аспирант Себряковского филиала Волгоградского государственного технического университета, Д. С. Андреев — преподаватель, кафедра «Математических и естественно-научных дисциплин», Себряковский филиал Волгоградского государственного технического университета, e-mail: [email protected], А. А. Пристансков -преподаватель, аспирант Себряковского филиала Волгоградского государственного технического университета, М. Н. Гулюкин - сотр. Лыткаринского завода оптического стекла, А. С. Белоусов - сотр. Лыткаринского завода оптического стекла, А. Н. Игнатов - сотр. Лыткаринского завода оптического стекла, Д. А. Храмогин - сотр. Лыткаринского завода оптического стекла, В.Т. Фомичёв — проф., д-р техн. наук, зав. каф. «Прикладная химия», Институт архитектуры и строительства Волгоградского государственного технического университета, [email protected], Х. С. Абзальдинов -канд. хим. наук, доц. каф. ТПМ КНИТУ, Г. Е. Заиков — д-р хим. наук, проф. каф. ТПМ КНИТУ.
