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Density functional theory, ab initio, and molecular mechanics calculations were used together with vibrational circular dichroism (VCD) and Fourier transform infrared spectroscopies. Calculations and experiments in solution show that the structure and the conformational energy profile of (\u2212)\u2010<jats:italic>S<\/jats:italic>\u2010nicotine are not strongly dependent on the medium, thus suggesting that the conformational equilibrium is dominated by hyperconjugative interactions rather than repulsive electronic effects. The analysis of the first recorded VCD spectra of (\u2212)\u2010<jats:italic>S<\/jats:italic>\u2010nicotine confirmed the presence of two main conformers at room temperature. Our results provide further evidence of the hypersensitivity of vibrational optical activity spectroscopies to the three\u2010dimensional structure of chiral samples and prove their suitability for the elucidation of solution\u2010state conformer distribution.<\/jats:p>","DOI":"10.1002\/cphc.201402652","type":"journal-article","created":{"date-parts":[[2014,11,24]],"date-time":"2014-11-24T09:32:51Z","timestamp":1416821571000},"page":"342-352","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Vibrational Circular Dichroism and Theoretical Study of the Conformational Equilibrium in (\u2212)\u2010<i>S<\/i>\u2010Nicotine"],"prefix":"10.1002","volume":"16","author":[{"given":"Pilar Gema Rodr\u00edguez","family":"Ortega","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Manuel","family":"Montejo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Juan Jesus L\u00f3pez","family":"Gonz\u00e1lez","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,11,24]]},"reference":[{"key":"e_1_2_7_1_2","volume-title":"Trease and Evans Pharmacognosy, 16th ed.","author":"Evans W. 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