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S QUANTUMCHEMICAL CALCULATION OF SOME DIOLS
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BY METHOD MNDO
Babkin Vladimir Aleksandrovich
Doctor of chemical sciences, professor of chair of mathematics and natural-science disciplines Sebryakovsky branch of the Volgograd State Architectural and Construction University, academician of the international academy of Sciences of "Kontenant" [email protected]
<j Michurina St. 21, 403343 Mikhailovka, Russian Federation
I
| Ignatov Alexey Viktorovich
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® Student of Sebryakovsky branch
^ Volgograd State Architectural and Construction University
■g Michurina St. 21, 403343 Mikhailovka, Russian Federation S
£ Zakharov Dmitry Sergeyevich
w
O Student of Sebryakovsky branch
§ Volgograd State Architectural and Construction University
Michurina St. 21, 403343 Mikhailovka, Russian Federation
Zaikov Gennady Efremovich
Doctor of chemical sciences, Professor, Head of Division of biological and chemical physics ^ of Polymer of The Federal State Budget Institution
of Science N.M. Emanuel Institute of Biochemical Physics <C [email protected]
§ Kosygina St. 4, 119334 Moscow, Russian Federation
C3 B
Fomichev Valery Tarasovich
^ Doctor of Technical sciences, professor, head of the department of the general and applied chemistry
3 Volgograd State Architectural and Construction University
© Akademicheskaia St. 1, 400074 Volgograd, Russian Federation
Belousov Andrey Sergeyevich
Engineer of Lytkarinsky plant of optical glass [email protected]
Parkovaia St. 1, 140080 Lytkarino, Russian Federation
Gulyukin Mikhail Nikolaevich
Chief of design-technology bureau Lytkarinsky plant of optical glass [email protected]
Parkovaia St. 1, 140080 Lytkarino, Russian Federation
Ignatov Alexander Nikolaevich Chief of scientific-industrial complex
Lytkarinsky plant of optical glass, Volgograd State Architecturally Building University,
Sebrykov departament
Parkovaia St. 1, 140080 Lytkarino, Russian Federation
Titova Evgenia Stanislavovna
Candidate of chemical sciences, associate professor Volgograd State Technical University [email protected]
Prospect Lenina, 28, 400005 Volgograd, Russian Federation
Abstract. Quantum chemical calculation of the molecules of 3,5-di(cyclo-trialumoxandiol)tetraalumoxantetraol-1,1,7,7and 1,7-di(cyclotrialumoxandiol)tetraalumoxantetraol-1,3,5,7 is executed for the first time by method MNDO with optimization of geometry on all parameters by standardgradient method. The optimized geometrical and electronic structure of these compounds is received. Acid force of 3,5-di(cyclo-trialumoxandiol) tetraalumoxantetraol-1,1,7,7and 1, 7-di(cyclotrialumoxandiol)tetraalumoxantetraol-1,3,5,7 is theoretically appreciated. It is established, that it to relate to a class of very weak H-acids (pKa=14) where pKa-universal index of acidity).
Key words: quantum chemical calculation, method MNDO,3,5-di(cyclo-trialumoxandiol)tetraalumoxantetraol-1,1,7,7, 1,7-di(cyclotrialumoxandiol)tetraalumoxantetraol-1,3,5,7, acid force.
The Aim of this work is a quantum chemical calculation and theoretically determination of acid force of derivativesdioles3,5-di(cyclotrialumoxandiol) tetraalumoxantetra-ol -1,1,7,7 and 1,7-di(cyclo trialumoxan-diol)tetraalumoxantetraol-1,3,5,7 by method MNDO with optimization of geometry on all parameters by standard gradient methodbuilt-in in PC GAMESS [10]. The calculation was executed in approach the insulated molecule in gas phase. Program MacMolPlt was used for visual presentation of models of molecules [9].These compounds can be fragments of polymermodels of optical glasses, such as «low-crownglass» and «heavyflint glass».
Results of the calculation
Optimized geometric and electronic structures, general and electronic energies of molecules3,5-di(cyclotrialumoxandiol)tetra-alumoxantetraol-1,1,7,7and 1,7-di(cyclo-trialumoxandiol)tetraalumoxantetraol-1,3,5,7 were received by method MNDO and are shown on fig. 1,2 and in tabl. 1-3. The universal factor of acidity was calculated for method MNDO by formula: pKa=42.11-147.18qmaxH+[1-8; 11] (where, qmaxH+ " a maximum positive charge on atom of the hydrogenqmaxH+= 0.19pKa- pKa-universal index of acidity (tabl.1).pKa = 14.
Fig. 1. Geometric and electronic structure of molecule of 3,5-di(cyclotrialumoxandiol)tetraalumoxantetraol -1,1,7,7.
(E0= -651635 kDg/mol, Eel= -3331183 kDg/mol)
Table 1
Optimized bond lengths, valence corners and charges on atoms of the molecul of 3,5-di(cyclotrialumoxandiol)tetraalumoxantetraol-1,1,7,7
Length of relations R,A Valent corners Degree Atom Charges on atoms of a molecule
O(2)-Al(1) 1.62 Al(1)-O(2)-Al(3) 179 Al(1) + 1.08
Al(3)-O(2) 1.64 O(2)-Al(3)-O(4) 120 O(2) -0.71
O(4)-Al(3) 1.63 Al(3)-O(4)-Al(5) 179 Al(3) +1.15
Al(5)-O(4) 1.63 O(4)-Al(5)-O(6) 120 O(4) -0.74
O(6)-Al(5) 1.64 Al(5)-O(6)-Al(7) 174 Al(5) +1.15
Al(7)-O(6) 1.62 O(6)-Al(7)-O(8) 121 O(6) -0.72
O(8)-Al(7) 1.67 O(6)-Al(7)-O(9) 122 Al(7) +1.07
O(9)-Al(7) 1.68 O(2)-Al(1)-O(10) 120 O(8) -0.55
O(10)-Al(1) 1.68 O(2)-Al(1)-O(11) 120 O(9) -0.56
O(11)-Al(1) 1.68 O(2)-Al(3)-O(12) 120 O(10) -0.56
O(12)-Al(3) 1.64 O(4)-Al(5)-O(13) 121 O(11) -0.56
O(13)-Al(5) 1.64 Al(3)-O(12)-Al(14) 179 O( 12) -0.72
Al(14)-O(12) 1.62 O(12)-Al(14)-O(15) 126 O(13) -0.72
O(15)-Al(14) 1.68 Al(14)-O(15)-Al(16) 131 Al(14) +1.07
Al(16)-O(15) 1.66 O(15)-Al(16)-O(17) 110 O(15) -0.71
O(17)-Al(16) 1.67 Al(16)-O(17)-Al(18) 129 Al(16) +1.02
Al(18)-O(17) 1.67 O(17)-Al(18)-O(19) 110 O( 17) -0.70
O(19)-Al(18) 1.66 O(15)-Al(16)-O(20) 125 Al(18) +1.02
O(20)-Al(16) 1.67 O(17)-Al(18)-O(21) 125 O(19) -0.70
O(21)-Al(18) 1.67 Al(5)-O(13)-Al(22) 179 O(20) -0.53
Al(22)-O(13) 1.62 O(13)-Al(22)-O(23) 126 O(21) -0.53
O(23)-Al(22) 1.67 Al(22)-O(23)-Al(24) 131 Al(22) +1.07
Al(24)-O(23) 1.66 O(23)-Al(24)-O(25) 110 O(23) -0.70
O(25)-Al(24) 1.67 Al(24)-O(25)-Al(26) 129 Al(24) +1.03
Al(26)-O(25) 1.67 O(25)-Al(26)-O(27) 110 O(25) -0.70
O(27)-Al(26) 1.66 O(23)-Al(24)-O(28) 125 Al(26) +1.02
O(28)-Al(24) 1.67 O(25)-Al(26)-O(29) 125 O(27) -0.71
O(29)-Al(26) 1.67 Al(7)-O(8)-H(30) 122 O(28) -0.53
H(30)-O(8) 0.93 Al(7)-O(9)-H(31) 123 O(29) -0.53
H(31)-O(9) 0.93 Al(1)-O( 10)-H(32) 124 H(30) +0.19
H(32)-O(10) 0.93 Al(1)-O(11)-H(33) 124 H(31) +0.19
H(33)-O(11) 0.93 Al(16)-O(20)-H(34) 122 H(32) +0.18
H(34)-O(20) 0.93 Al(18)-O(21)-H(35) 122 H(33) +0.18
H(35)-O(21) 0.93 Al(24)-O(28)-H(36) 122 H(34) +0.19
H(36)-O(28) 0.93 Al(26)-O(29)-H(37) 122 H(35) +0.19
Table 2
Optimized bond lengths, valence corners and charges on atoms of the molecule of 1,7-di(cyclotrialumoxandiol)tetraalumoxantetraol-1,3,5,7
Length of relations R,A Valent corners Degree Atom Charges on atoms of a molecule
O(2)-Al(1) 1.63 Al(1)-O(2)-Al(3) 178 Al(1) + 1.11
Al(3)-O(2) 1.63 O(2)-Al(3)-O(4) 121 O(2) -0.73
O(4)-Al(3) 1.64 Al(3)-O(4)-Al(5) 170 Al(3) + 1.10
Al(5)-O(4) 1.64 O(4)-Al(5)-O(6) 121 O(4) -0.74
O(6)-Al(5) 1.63 Al(5)-O(6)-Al(7) 175 Al(5) +1.10
Al(7)-O(6) 1.64 O(6)-Al(7)-O(8) 121 O(6) -0.73
O(8)-Al(7) 1.63 O(6)-Al(7)-O(9) 120 Al(7) +1.11
O(9)-Al(7) 1.68 0(2)-Al(1)-0(10) 121 O(8) -0.70
O(10)-Al(1) 1.63 O(2)-Al(1)-O(11) 121 O(9) -0.56
O(11)-Al(1) 1.68 O(2)-Al(3)-O(12) 119 O(10) -0.70
O(12)-Al(3) 1.68 O(4)-Al(5)-O(13) 120 O(11) -0.56
O(13)-Al(5) 1.68 Al(1)-0(10)-Al(14) 178 O(12) -0.56
Al(14)-O(10) 1.62 O(10)-Al(14)-O(15) 126 O(13) -0.56
O(15)-Al(14) 1.68 Al(14)-O(15)-Al(16) 131 Al(14) +1.08
Al(16)-O(15) 1.67 O(15)-Al(16)-O(17) 110 O(15) -0.71
O(17)-Al(16) 1.67 Al(16)-O(17)-Al(18) 130 Al(16) +1.02
Al(18)-O(17) 1.67 O(17)-Al(18)-O(19) 110 O(17) -0.70
O(19)-Al(18) 1.66 O(15)-Al(16)-O(20) 125 Al(18) +1.03
O(20)-Al(16) 1.67 O(17)-Al(18)-O(21) 125 O(19) -0.70
O(21)-Al(18) 1.67 Al(7)-O(8)-Al(22) 177 O(20) -0.53
Al(22)-O(8) 1.62 O(8)-Al(22)-O(23) 125 O(21) -0.53
O(23)-Al(22) 1.67 Al(22)-O(23)-Al(24) 131 Al(22) +1.08
Al(24)-O(23) 1.66 O(23)-Al(24)-O(25) 110 O(23) -0.70
O(25)-Al(24) 1.67 Al(24)-O(25)-Al(26) 130 Al(24) +1.03
Al(26)-O(25) 1.67 O(25)-Al(26)-O(27) 110 O(25) -0.70
O(27)-Al(26) 1.67 O(23)-Al(24)-O(28) 125 Al(26) +1.03
O(28)-Al(24) 1.67 O(25)-Al(26)-O(29) 125 O(27) -0.71
O(29)-Al(26) 1.67 Al(5)-O(13)-H(30) 123 O(28) -0.53
H(30)-O(13) 0.93 Al(7)-O(9)-H(31) 123 O(29) -0.53
H(31)-O(9) 0.93 Al(3)-O(12)-H(32) 123 H(30) +0.18
H(32)-O(12) 0.93 Al(1)-O(11)-H(33) 123 H(31) +0.18
H(33)-O(11) 0.93 Al(16)-O(20)-H(34) 122 H(32) +0.18
H(34)-O(20) 0.93 Al( 18)-O(21)-H(35) 122 H(33) +0.19
H(35)-O(21) 0.93 Al(24)-O(28)-H(36) 122 H(34) +0.19
H(36)-O(28) 0.93 Al(26)-O(29)-H(37) 122 H(35) +0.19
Table 3
General energy ^^ electronic energy Œ^), maximum positive charge on atom of the hydrogen (qmaxH+), the universal factor of acidityderivativesdioles-monomersofcationicpolymerization
№ Monomer E0kDg/mol Eel= kDg/mol a H+ nmax рКа
1 3,5-di(cyclotrialumoxandiol) tetraalumoxantetraol-1,1,7,7 -651 635 -3 331 183 +0,19 14
2 1,7- di cyclotrialumoxandiol) tetraalumoxantetraol -1,3,5,7 -651 646 -3 399 236 +0,19 14
Fig. 2. Geometric and electronic structure of molecule of 1,7-di(cyclotrialumoxandiol) tetraalumoxantetraol-1,3,5,7
(E0= -651646 kDg/mol, Eel= -3399236 kDg/mol)
Quantum-chemical calculation of molecules 3,5-di(cyclotrialumoxandiol)tetra-alumoxantetraol-1,1,7,7 and 1,7-di(cyclotrialumoxandiol)tetraalumoxantetraol-1,3,5,7 by method MNDO was executed for the first time. Optimized geometric and electronic structures of these compounds were received. Acid power of moleculesterpenes was theoretically evaluated (pKa = 14). These compounds pertain to class ofvery weak H-acids (pKa = 14).
REFERENCES
1. Babkin V.A., Andreev D. S., ^tova Е. S., Dmitriev V.U., Fomichev VT, Zaikov G. E. Theoretical Estimation of Acidic Force of Linear Olefins of Cationic Polymerization. N. Y., Nova Publisher, 2011, 65 p.
2 Babkin V.A., AndreevD.S. Quantum-chemical calculation of molecule 2-ethylbutene-1 by method MNDO. Collection of research paper: Quantum-chemical calculation of unique molecular systems. Volgograd, VolGU publ., 2010, vol. 1, p. 176-185.
3. Babkin V.A., Andreev D.S., Fomichev VT, Dmitriev VYu. Quantum-chemical calculation of linear and branchy monomers of cationic polymerization. Volgograd, VolGU publ., 2011, 65 p.
4. Babkin V.A., Andreev D.S., Titovav E.S., Sangalov Yu.А., Denisov А.А. Quantum-chemical
calculation of alicyclicolefins and their derivations. Volgograd, VolGU publ., 2012, 100 p.
5. Babkin V.A., Andreev D.S., Тitova Е. S., Potapov S.S., Sangalov Yu.А. Quantum-chemical calculation of isoolefinsanddienes. Volgograd, VolGU publ., 2011, 71 p.
6. Babkin V.A., Dmitriev V.Yu., Savin G.A., Zaikov G.E., RakhimovA.I. Quantum-chemical aspects of mechanism acylation of bicyclophosphits by chloranhydrides of carboxylic acid. Volgograd, VolGU publ., 2011, 91 p.
7. Babkin V.A., Dmitriev V.Yu., Zaikov G.E. Quantum-chemical calculation of molecule monomer of cationic polymerizationhexene-1 by method MNDO. Collection of research paper: Quantum-chemical calculation of unique molecular systems. Volgograd, VolGU publ., 2010, vol. 1, p. 93-104.
8. Babkin V.A., Fedunov R.G., Minsker K.S. Oxidation communication, 2002, №> 1, 25, p. 21-47.
9. Bode B.M., Gordon M.S., Mol J. Graphics Mod, 1998, 16, p. 133-138.
10. Shmidt M.W., Baldrosge K.K., Elbert J.A., Gordon M.S., Enseh J.H., Koseki N., Matsvnaga K.A. Nguyen S.J. SU, and anothers. J. Comput. Chem. 14, 1993, p. 1347-1363.
11. Вabkin V.A., Zaikov G.E. Nobel laureats and nanotechnologgy of the applaed quantum chemistry. USA. N.Y., Nova Science Publisher, 2010, pp. 351
КВАНТОВО-ХИМИЧЕСКИЙ РАСЧЕТ НЕКОТОРЫХ ДИОЛОВ
МЕТОДОМ MNDO
Бабкин Владимир Александрович
Доктор химических наук, профессор кафедры математики и естественнонаучных дисциплин Себряковского филиала Волгоградского государственного архитектурно-строительного университета, академик международной академии наук «Контенант» [email protected]
ул. Мичурина, 21, 403343 г. Михайловка, Российская Федерация
Игнатов Алексей Викторович
Студент Себряковского филиала
Волгоградского государственного архитектурно-строительного университета [email protected]
ул. Мичурина, 21, 403343 г. Михайловка, Российская Федерация
Захаров Дмитрий Сергеевич
Студент Себряковского филиала
Волгоградского государственного архитектурно-строительного университета [email protected]
ул. Мичурина, 21, 403343 г. Михайловка, Российская Федерация
Заиков Геннадий Ефремович
Доктор химических наук, профессор,
заведующий отделом биологической и химической физики полимеров Федерального государственного бюджетного учреждения науки Институт биохимической физики им. Н.М. Эмануэля РАН chembio@sky. ЛрЬ ras.ru
ул. Косыгина, 4, 119334 г. Москва, Российская Федерация
Фомичев Валерий Тарасович
Доктор технических наук, профессор, заведующий кафедрой общей и прикладной химии Волгоградского государственного архитектурно-строительного университета [email protected]
ул. Академическая, 1, 400074 г. Волгоград, Российская Федерация
Белоусов Андрей Сергеевич
Инженер Лыткаринского завода оптического стекла [email protected]
ул. Парковая, 1, 140080 г. Лыткарино, Российская Федерация
Гулюкин Михаил Николаевич
Начальник конструкторско-технологического бюро Лыткаринского завода оптического стекла [email protected]
ул. Парковая, 1, 140080 г. Лыткарино, Российская Федерация
Игнатов Александр Николаевич
Начальник научно-производственного комплекса Лыткаринского завода оптического стекла [email protected]
ул. Парковая, 1, 140080 г. Лыткарино, Российская Федерация
Титова Евгения Станиславовна
Кандидат химических наук, доцент
Волгоградского государственного технического университета [email protected]
Проспект Ленина, 28, 400005 г. Волгоград, Российская Федерация
Аннотация. Квантово-химическое вычисление молекул 3,5-^ (сус^-trialumoxandiol) tetraalumoxantetraol-1,1,7,7 и 1,7^ (cyclotrialumoxandiol) tetraalumoxantetraol-1,3,5,7 выполнен впервые методом MNDO с оптимизацией геометрии на всех параметрах предлагаемым методом. Получена оптимизированная геометрическая и электронная структура этих составов. Теоретически оценена кислотная сила 3,5^ (cyclo-trialumoxandiol) tetraalumoxantetraol-1,1,7,7 и 1,7-& (cyclotrialumoxandiol) tetraalumoxantetraol-1,3,5,7. Установлено, что эта молекула относится к классу очень слабых кислот (рКя>14) , где р^-универсальный индекс кислотности).
Ключевые слова: квантово- химическое вычисление, метод MNDO, 3,5^ ^у^-trialumoxandiol) tetraalumoxantetraol-1,1,7,7, 1,7-& (cyclotrialumoxandiol) tetraalumoxantetraol-1,3,5,7, кислотная сила.
