The optical absorption spectra of a number of compounds containing carbonyl groups in solutions of n-hexane and methanol are considered. It is shown that the specific effect of the polar solvent is due to the formation of hydrogen bonds between the solvent molecules and within the molecule under study. As a result, we observe a change in the energy gap between the corresponding occupied and unoccupied molecular orbitals.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Reichardt, C. and Welton, T., Solvents and Solvent Effects in Organic Chemistry, Weinheim: Wiley, 2011.
Brealey, G.J. and Kasha, M., J. Am. Chem. Soc., 1955, vol. 77, no. 17, p. 4462.
Exner, O., Dipole Moments in Organic Chemistry, Stuttgart: G. Thieme, 1975.
Tseplin, E.E., Tseplina, S.N., and Khvostenko, O.G., Opt. Spectrosc., 2018, vol. 125, no. 4, p. 506.
Becker, R.S., J. Mol. Spectrosc., 1959, vol. 3, p. 1.
Tseplin, E.E., Tseplina, S.N., and Khvostenko, O.G., Opt. Spectrosc., 2011, vol. 110, no. 6, p. 903.
Tseplin, E.E., Tseplina, S.N., and Khvostenko, O.G., Opt. Spectrosc., 2016, vol. 120, no. 2, p. 274.
Tseplina, S.N. and Tseplin, E.E., Izv. Ufim. Nauchn. Tsentra, Ross. Akad. Nauk, 2015, no. 4, p. 38.
Tseplina, S.N., Transformation of the spectroscopic states of electronically excited molecules during singlet-triplet intercombination conversion, Cand. Sci. (Phys.–Math.) Dissertation, Ufa: Inst. Mol. Crystal Phys., Ufa Fed. Res. Center, Russ. Acad. Sci., 2016.
Tseplin, E.E. and Tseplina, S.N., Chem. Phys. Lett., 2019, vol. 716, p. 142.
Frisch, M.J., Trucks, G.W., Schlegel, H.B., et al., Gaussian 09, Revision C.01, Wallingford, CT: Gaussian, 2009.
Tomasi, J., Mennucci, B., and Cammi, R., Chem. Rev., 2005, vol. 105, no. 8, p. 2999.
De Vetta, M., Menger, M.F.S.J., Nogueira, J.J., and González, L., J. Phys. Chem. B, 2018, vol. 122, no. 11, p. 2975.
Improta, R. and Barone, V., J. Am. Chem. Soc., 2004, vol. 126, no. 44, p. 14320.
This work was performed on equipment at the Spectrum shared resource center of the Institute of Molecular and Crystal Physics. The authors also thank the Chemistry shared resource center of the Ufa Institute of Chemistry for allowing us to use its supercomputer for quantum chemical calculations.
This work was performed as part of State Task no. AAAA19-119022290052-9.
Translated by V. Alekseev
About this article
Cite this article
Tseplin, E.E., Tseplina, S.N. & Khvostenko, O.G. Orbital Mechanism of the Specific Effect of a Polar Solvent in Optical Absorption Spectra. Bull. Russ. Acad. Sci. Phys. 84, 559–562 (2020). https://doi.org/10.3103/S1062873820050366