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Solvent Effects on IR Modes of (R)-3-Methylcyclopentanone Conformers: A Computational Investigation

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Abstract

Density Functional Theory (DFT) calculations of infrared spectra for the optimized geometries of the R-(+)-3-methylcyclopentanone (R3MCP) equatorial-methyl and axial-methyl conformers were performed in eleven common solvents with a wide polarity range, within the framework of polarizable continuum model (PCM). The DFT correlation function type B3LYP, using a powerful basis set (aug-cc-pVDZ), yielded different linear correlations between solvent polarity and R3MCP equatorial and axial conformers for frequencies of IR modes, intensities, and enthalpies. DFT calculations of the dipole moments of R3MCP equatorial and axial conformer components in 3D were also carried out and found to have a linear correlation with the solvent polarity. An increasing trend for the hypsochromic (blue) shift in the equatorial conformer’s IR frequencies is observed, in comparison to bathochromic (red) shift for the axial-methyl conformer IR modes, as a function of the solvent polarity.

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References

  1. Richardson, F.S., Shillady, D.D., Bloor, J.E.: The optical activity of alkyl-substituted cyclopentanones. INDO molecular orbital model. J. Phys. Chem. 75, 2466–2479 (1971)

    Article  CAS  Google Scholar 

  2. Flament, J.P., Gervais, H.P.: Optical-activity of 3-methyl-cyclopentanone—ab initio calculation. Tetrahedron 36, 1949–1952 (1980)

    Article  CAS  Google Scholar 

  3. Li, Y.S.: Microwave-spectrum, dipole-moment, and conformation of 3-methylcyclopentanone. J. Mol. Spectrosc. 104, 302–307 (1984)

    Article  CAS  Google Scholar 

  4. Potts, A.R., Nesselrodt, D.R., Baer, T., Driscoll, J.W., Bays, J.P.: The 3s Rydberg spectra and conformations of methyl-substituted cyclopentanones. J. Phys. Chem. 99, 12090–12098 (1995)

    Article  CAS  Google Scholar 

  5. He, J., Petrovic, A.G., Polavarapu, P.L.: Determining the conformer populations of (R)-(+)-3-methylcyclopentanone using vibrational absorption, vibrational circular dichroism, and specific rotation. J. Phys. Chem., B 108, 20451–20457 (2004)

    Article  CAS  Google Scholar 

  6. Li, R., Sullivan, R., Al-Basheer, W., Pagni, R.M., Compton, R.N.: Linear and nonlinear circular dichroism of R-(+)-3-methylcyclopentanone. J. Chem. Phys. 125, 144304 (2006)

    Article  CAS  Google Scholar 

  7. Al-Basheer, W., Pagni, R.M., Compton, R.N.: Spectroscopic and theoretical investigation of (R)-3-methylcyclopentanone. The effect of solvent and temperature on the distribution of conformers. J. Phys. Chem., A 111, 2293–2298 (2007)

    Article  CAS  Google Scholar 

  8. Kim, D., Baer, T.: Gas-phase measurement of ΔH ∘ between axial and equatorial conformations of 3-methylcyclopentanone. Chem. Phys. 256, 251–258 (2000)

    Article  CAS  Google Scholar 

  9. Lee, C., Yang, W., Parr, R.G.: Development of the Colle–Salvetti correlation-energy formula into a functional of the electron-density. Phys. Rev., B 37, 785–789 (1988)

    Article  CAS  Google Scholar 

  10. Parr, R.G., Yang, W.: Density Functional Theory of Atoms and Molecules. Oxford University Press, New York (1989)

    Google Scholar 

  11. Becke, A.D.: Density functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993)

    Article  CAS  Google Scholar 

  12. Onsager, L.: Electric moments of molecules in liquids. J. Am. Chem. Soc. 58, 1486–1493 (1936)

    Article  CAS  Google Scholar 

  13. Bauer, E., Magat, M.: Regarding the deformation of molecules in a condensed phase, and the “hydrogen bond”. J. Phys. Radium 9, 319–330 (1938)

    Article  CAS  Google Scholar 

  14. Hirota, E.: The electrostatic effect of the solvents on the frequency shifts and the intensity changes of the infrared absorption spectra. Bull. Chem. Soc. Jpn. 27, 295–297 (1954)

    Article  CAS  Google Scholar 

  15. Mallard, W.C., Straley, J.W.: Vibrational intensities in halogenated methanes. III. The interpretation of solution data. J. Chem. Phys. 27, 877–879 (1957)

    Article  CAS  Google Scholar 

  16. Person, W.B.: Liquid–gas infrared intensities, pressure-induced absorption, and the temperature dependence of infrared intensities in liquids. J. Chem. Phys. 28, 319–322 (1958)

    Article  CAS  Google Scholar 

  17. Buckingham, A.D.: Solvent effects in infra-red spectroscopy. Proc. R. Soc. Lond. Ser. A, Math. Phys. Sci. 248, 169–182 (1958)

    Article  CAS  Google Scholar 

  18. Buckingham, A.D.: A theory of frequency, intensity and band-width changes due to solvents in infra-red spectroscopy. Proc. R. Soc. Lond. Ser. A, Math. Phys. Sci. 255, 32–39 (1960)

    Article  CAS  Google Scholar 

  19. Mirone, P.: Solvent effects on Raman and infra-red intensities in continuous dielectric model. Spectrochim. Acta 22, 1897–1905 (1966)

    Article  CAS  Google Scholar 

  20. Miertus, S., Scrocco, E., Tomasi, J.: Electrostatic interaction of a solute with a continuum. A direct utilization of ab initio molecular potentials for the prevision of the solvent effects. Chem. Phys. 55, 117–129 (1981)

    Article  CAS  Google Scholar 

  21. Cammi, R., Cappelli, C., Corni, S., Tomasi, J.: On the calculation of infrared intensities in solution within the polarizable continuum model. J. Phys. Chem., A 104, 9874–9879 (2000)

    Article  CAS  Google Scholar 

  22. Rizzo, A., Lin, N., Ruud, K.: Ab initio study of the one- and two-photon circular dichroism of R-(+)-3-methylcyclopentanone. J. Chem. Phys. 128, 164312 (2008)

    Article  Google Scholar 

  23. Pipolo, S., Cammi, R., Rizzo, A., Cappelli, C., Mennucci, B., Tomasi, J.: Cavity field effects within a polarizable continuum model of solvation: application to the calculation of electronic circular dichroism spectra of R-(+)-3-methylcyclopentanone. Int. J. Quant. Chem. 111, 826–838 (2011)

    Article  CAS  Google Scholar 

  24. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, J.A., Jr., Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M., Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J.E., Hratchian, H.P., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Ayala, P.Y., Morokuma, K., Voth, G.A., Salvador, P., Dannenberg, J.J., Zakrzewski, V.G., Dapprich, S., Daniels, A.D., Strain, M.C., Farkas, O., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Ortiz, J.V., Cui, Q., Baboul, A.G., Clifford, S., Cioslowski, J., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Gonzalez, C., Pople, J.A.: Gaussian 03, Revision B.03. Gaussian, Inc., Pittsburgh (2003)

    Google Scholar 

  25. Scott, A.P., Radom, L.: Harmonic vibrational frequencies: an evaluation of Hartree–Fock, Moller–Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors. J. Phys. Chem. 100, 16502–16513 (1996)

    Article  CAS  Google Scholar 

  26. Miertus, S., Tomasi, J.: Approximate evaluations of the electrostatic free-energy and internal energy changes in solution processes. Chem. Phys. 65, 239–245 (1982)

    Article  CAS  Google Scholar 

  27. Cossi, M., Barone, V., Cammi, R., Tomasi, J.: Ab initio study of solvated molecules: A new implementation of the polarizable continuum model. Chem. Phys. Lett. 255, 327–335 (1996)

    Article  CAS  Google Scholar 

  28. Dimroth, K., Reichardt, C., Siepmann, T., Bohlmann, F.: Uber Pyridinium-n-phenol betaine und ihre verwendung zur charakterisierung der polaritat von losungsmitteln. Liebigs Ann. Chem. 661, 1–37 (1963)

    Article  CAS  Google Scholar 

  29. Kamlet, M.J., Abboud, J.L., Taft, R.W.: Solvatochromic comparison method. 6. π ∗ of solvent polarities. J. Am. Chem. Soc. 99, 6027–6038 (1977)

    Article  CAS  Google Scholar 

  30. Reichardt, C.: Solvatochromism, thermochromism, piezochromism, halochromism, and chiro-solvatochromism of pyridinium N-phenoxide betaine dyes. Chem. Soc. Rev. 21, 147–153 (1992)

    Article  CAS  Google Scholar 

  31. Reichardt, C.: Solvents and Solvent Effects in Organic Chemistry, 3rd edn. Wiley-VCH, Weinheim (2003)

    Google Scholar 

  32. Marcus, Y.: The Properties of Solvents. Wiley, Chichester (1998)

    Google Scholar 

Download references

Acknowledgements

This work is dedicated to the memory of Mississippi State University physics graduate student Shereen Shawaqfeh whose life ended prematurely in a tragic car accident on September 18, 2010. Shereen was a friend, a fine scholar, and a colleague at the Hashemite University in Jordan. Her enthusiasm, dedication, and commitment to pursue a career in science continues to inspire many women.

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  1. Center for Atmospheric Research Experiments, Environment Canada, Egbert, ON, L0L 1N0, Canada

    Watheq Al-Basheer

  2. Department of Physics, University of Tennessee, Knoxville, TN, 37996, USA

    Watheq Al-Basheer

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  1. Watheq Al-Basheer
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Correspondence to Watheq Al-Basheer.

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Al-Basheer, W. Solvent Effects on IR Modes of (R)-3-Methylcyclopentanone Conformers: A Computational Investigation. J Solution Chem 41, 1495–1506 (2012). https://doi.org/10.1007/s10953-012-9890-8

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