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All solution-phase measurements of optical rotatory dispersion (ORD) revealed plain-looking curves of uniformly negative polarity in the near-ultraviolet\/visible regions, while their solvent-free counterpart showed evidence of a zero-crossing that would lead to positive rotatory powers for wavelengths \u2264350 nm. A variety of quantum-chemical paradigms built upon density-functional (dispersion-corrected B3LYP and cam-B3LYP) and coupled cluster (CCSD) levels of theory were enlisted to explore the structural and response characteristics of stationary points within the ground electronic state of S-2-MeAz. Two stable conformations possessing distinct orientations of the amino (N\u2013H) moiety with respect to the methyl substituent on the aziridine ring were identified, with the C1 (trans or anti) isomer, which is the global-minimum of energy in all media, predicted to have wavelength-resolved positive specific rotations that were 2\u20133 times smaller in magnitude than the corresponding negative values of the higher-lying C2 (cis or syn) form. The antagonistic chiroptical signatures of these species were merged under the independent-conformer ansatz by using ambient (T = 300 K) population fractions derived from various relative internal-energy (without and with vibrational zero-point offsets) and free-energy metrics. For isolated (vapor-phase) S-2-MeAz molecules, quantitative agreement between theory and experiment was attained by combining ensemble-averaged CCSD calculations of purely electronic optical activity (EOA) evoked from the static equilibrium configurations of C1 and C2 with commensurate harmonic and anharmonic nuclear contributions to vibronically-\/vibrationally-induced optical activity (V2OA). Detailed analyses found essentially all 27 modes of each conformer to participate actively without any particular motions of the molecular framework dominating. In contrast, attempts to model condensed-phase behavior based on the conformer structures, energies, and response-properties (viz., EOA) emerging from PCM and SMD implicit-solvation treatments failed to reproduce the overall shapes of observed ORD profiles, thereby suggesting that other neglected factors (e.g., explicit solute\u2013solvent interactions) may be at play.<\/jats:p>","DOI":"10.1021\/acs.jpca.6c04767","type":"journal-article","created":{"date-parts":[[2026,10,12]],"date-time":"2026-10-12T15:03:04Z","timestamp":1791817384000},"page":"8301-8324","source":"Crossref","is-referenced-by-count":0,"title":["Dispersive Optical\nActivity of (\n                    <i>S<\/i>\n                    )-2-Methylaziridine:\nIntrinsic Properties and Extrinsic Solvation\nEffects"],"prefix":"10.1021","volume":"130","author":[{"given":"Thomas P.","family":"Regan","sequence":"first","affiliation":[{"name":"Yale University , , P.O. Box 208107, , ,","place":["New Haven, Connecticut, United States, 06520-8107"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Clayton L.","family":"Craft","sequence":"additional","affiliation":[{"name":"Yale University , , P.O. Box 208107, , ,","place":["New Haven, Connecticut, United States, 06520-8107"]},{"name":"Information and Spectrum Warfare Directorate Air Force Research Laboratory , , ,","place":["Rome, New York, United States, 13441"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7178-7638","authenticated-orcid":true,"given":"Patrick H.","family":"Vaccaro","sequence":"additional","affiliation":[{"name":"Yale University , , P.O. Box 208107, , ,","place":["New Haven, Connecticut, United States, 06520-8107"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,12]]},"reference":[{"key":"2026102208071264700_cit1","doi-asserted-by":"crossref","DOI":"10.1017\/CBO9780511535468","volume-title":"Molecular Light Scattering\nand Optical Activity","author":"Barron","year":"2004","edition":"2"},{"key":"2026102208071264700_cit2","first-page":"275","article-title":"Optical Rotation\nand Intrinsic Optical Activity","volume-title":"Comprehensive\nChiroptical Spectroscopy","author":"Vaccaro","year":"2012"},{"key":"2026102208071264700_cit3","doi-asserted-by":"crossref","DOI":"10.1002\/9781118120392","volume-title":"Comprehensive Chiroptical\nSpectroscopy","author":"Berova","year":"2012"},{"key":"2026102208071264700_cit4","volume-title":"Optical Rotatory Power","author":"Lowry","year":"1935"},{"key":"2026102208071264700_cit5","doi-asserted-by":"publisher","first-page":"185","DOI":"10.1016\/S0065-3276(05)50009-1","article-title":"The Ab Initio Calculation of Optical Rotation and Electronic Circular\nDichroism","volume":"50","author":"Pecul","year":"2005","journal-title":"Adv. Quantum Chem."},{"key":"2026102208071264700_cit6","doi-asserted-by":"publisher","first-page":"12057","DOI":"10.1021\/jp075046u","article-title":"The Current\nState of Ab Initio Calculations\nof Optical Rotation and Electronic Circular Dichroism Spectra","volume":"111","author":"Crawford","year":"2007","journal-title":"J. Phys. Chem. A"},{"key":"2026102208071264700_cit7","doi-asserted-by":"publisher","first-page":"E116","DOI":"10.1002\/chir.20789","article-title":"Computing\nChiroptical Properties with First-Principles Theoretical Methods:\nBackground and Illustrative Examples","volume":"21","author":"Autschbach","year":"2009","journal-title":"Chirality"},{"key":"2026102208071264700_cit8","doi-asserted-by":"publisher","first-page":"399","DOI":"10.1146\/annurev-physchem-052516-044827","article-title":"Calculating Natural Optical Activity of Molecules from\nFirst Principles","volume":"68","author":"Srebro-Hooper","year":"2017","journal-title":"Annu. Rev. Phys. 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Soc.\nJpn."},{"key":"2026102208071264700_cit33","doi-asserted-by":"publisher","first-page":"1324","DOI":"10.1021\/j100290a011","article-title":"A Circular Dichroism Study of the Oxirane Chromophore","volume":"91","author":"Gedanken","year":"1987","journal-title":"J. Phys. Chem. A"},{"key":"2026102208071264700_cit34","doi-asserted-by":"publisher","first-page":"477","DOI":"10.1016\/0009-2614(91)85153-N","article-title":"Experimental and Quantum-Theoretical\nInvestigation of the Circular Dichroism Spectrum of R-Methyloxirane","volume":"180","author":"Carnell","year":"1991","journal-title":"Chem. Phys. Lett."},{"key":"2026102208071264700_cit35","doi-asserted-by":"publisher","first-page":"539","DOI":"10.1080\/00268979400100404","article-title":"Experimental Circular Dichroism and\nVUV Spectra of Substituted Oxiranes and Thiiranes","volume":"82","author":"Breest","year":"1994","journal-title":"Mol. 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Lett."},{"key":"2026102208071264700_cit42","doi-asserted-by":"publisher","first-page":"3550","DOI":"10.1063\/1.1772352","article-title":"Coupled Cluster\nCalculations of Optical\nRotatory Dispersion of (S)-Methyloxirane","volume":"121","author":"Tam","year":"2004","journal-title":"J.\nChem. Phys."},{"key":"2026102208071264700_cit43","doi-asserted-by":"publisher","first-page":"385","DOI":"10.1016\/j.cplett.2004.11.082","article-title":"Coupled Cluster\nCalculations of the Optical Rotation\nof S-Propylene Oxide in Gas Phase","volume":"401","author":"Kongsted","year":"2005","journal-title":"Chem. Phys. Lett."},{"key":"2026102208071264700_cit44","doi-asserted-by":"publisher","first-page":"3594","DOI":"10.1002\/anie.200500642","article-title":"The Importance of Molecular Vibrations:\nThe Sign Change\nof the Optical Rotation of Methyloxirane","volume":"44","author":"Ruud","year":"2005","journal-title":"Angew.\nChem., Int. 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Theory Comput."},{"key":"2026102208071264700_cit48","doi-asserted-by":"publisher","first-page":"3424","DOI":"10.1021\/jz401854y","article-title":"Anharmonicity Effects\nin the Vibrational CD Spectra of Propylene Oxide","volume":"4","author":"Merten","year":"2013","journal-title":"J. Phys. Chem.. Lett."},{"key":"2026102208071264700_cit49","doi-asserted-by":"publisher","first-page":"196","DOI":"10.1364\/OME.5.000196","article-title":"Optical Rotatory Dispersion of Methyoxirane\nin Aqueous Solution: Assessing the Performance of Density Functional\nTheory in Combination with a Fully Polarizable QM\/MM\/PCM Approach","volume":"5","author":"Egidi","year":"2015","journal-title":"Opt. Mater. 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