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Babkov L. M., Davydova N. A., Moisejkina E. A. Hydrogen Bonding and its Influence on the Structure and Vibrational Spectra of Cyclohexanol. Izvestiya of Saratov University. Physics , 2013, vol. 13, iss. 1, pp. 13-26. DOI: 10.18500/1817-3020-2013-13-1-13-26

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Hydrogen Bonding and its Influence on the Structure and Vibrational Spectra of Cyclohexanol

Babkov Lev Mikhailovich, Saratov State University
Davydova Nadezhda Aleksandrovna, Institute of Physics, National Academy of Sciences of Ukraine
Moisejkina Elena Aleksandrovna, Saratov State University

In the range of 600–3600 cm–1 in a wide range of temperatures, in different phase states (plastic phase I, the crystalline phase II and III) IR spectra of cyclohexanol have been measured. Using method of density functional theory (B3LYP) in the basis of 6-31G (d) the structural-dynamic models of conformers of cyclohexanol molecules differing from each other by orientation of hydroxyl group relatively carbonic ring and H-complexes with different structures, which presumably realized in polymorphic modification of cyclohexanol, have been constructed. Energies, structures, dipole moments, polarizability, the normal frequencies in the harmonic approximation and the intensity distribution in the vibrational spectra have been calculated. The spectral – structural features of different H-complexes have been determined. This allows to refine the interpretation of the vibrational spectra and to establish a correspondence between the H-complex and different polymorphic modifications of cyclohexanol.

  1. Бабков Л. М., Давыдова Н. А., Моисейкина Е. А. ИК спектры циклогексанола и структурно-динамическая модель молекулы // Изв. Сарат. ун-та. Нов. сер. 2012. Сер. Физика. Т. 12, вып.1. С. 54–62.
  2. Kelley K. K. Cyclohexanol and the third law of thermodynamics // J. Amer. Chem. Soc. 1929. Vol. 51. P. 1400–1406.
  3. Neelakantan R. Raman spectra of cyclohexanol // Proc. Mathematical Sciences. 1963. Vol. 57. P. 94–102.
  4. Green J. R., Griffi th W. T. Phase transformations in solid cyclohexanol // J. Phys. Chem. Solids. 1965.Vol. 26. P. 631–637.
  5. Adachi K., Suga H., Seki S. Phase changes in crystalline and glassy-crystalline cyclohexanol // Bull. Chem. Soc. Jpn. 1968. Vol. 41. P. 1073–1087.
  6. Wunderlich B. The detection of conformational disorder by thermal analysis // Pure & Appl. Chem. 1989. Vol. 61, № 8. P. 1347–1351.
  7. Inscore F., Gift A., Maksymiuk P., Farquharson S. Characterization of chemical warfare G-agent hydrolysis products by surface-enhanced Raman spectroscopy // SPIE. 2004. Vol. 5585. P. 46–52.
  8. Bonnet A., Chisholm J., Sam Motherwell W. D., Jones W. Hydrogen bonding preference of equatorial versus axial hydroxyl groups in pyran and cyclohexane rings in organic crystals // Cryst. Eng. Comm. 2005. Vol. 7, № 9. P. 71–75.
  9. Ibberson R. M., Parsons S., Allan D. R., Bell T. Polymorphism in cyclohexanol // Acta Cryst. 2008. B. 64. Р. 573–582.
  10. Элькин П. М., Шальнова Т. А., Гордеев И. И. Структурно-динамические модели конформеров циклогексанола // Прикаспийский журнал : управление и высокие технологии. 2010. Т. 11, № 3. С. 41–45.
  11. Кон В. Электронная структура вещества – волновые функции и функционалы плотности // УФН. 2002. Т. 172, № 3. С. 336–348.
  12. Попл Дж. А. Квантово-химические модели // УФН. 2002. Т. 172, № 3. С. 349–356.
  13. Frisch J., Trucks G. W., Schlegel H. B. et al. Gaussian 03, Revision B.03 / Gaussian Inc. Pittsburgh, 2003. 302 p.
  14. Иогансен А. В. Инфракрасная спектроскоия и спектральное определение энергии водородной связи // Водородная связь / ред. Н. Д. Соколов. М. : Наука, 1981. С. 112–155.