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In aqueous solution the thione forms, Thione(N1,N7) and Thione(N1,N9), are the only thermally accessible species, whereas the thiol forms are significantly less stable. X-ray derived dimeric models provide closer agreement with spontaneous Raman spectrum, showing that intermolecular interactions are essential for describing the solid-state spectrum; for the best Thione(N1,N9) dimer, the mean deviation is 1.1 \u00b1 0.6%. For the adsorbed species, calculations on a tetrahedral Au20 cluster reveal that the thermodynamically preferred flat configurations do not provide the best match to the experimental SERS spectrum, which is instead more accurately reproduced by sulfur-bound vertex and center motifs. Increasing surface coverage and mixed-tautomer adsorption are further required to recover the experimental relative intensities, with a 3:1 Thione(N1,N9)\/Thione(N1,N7) model giving the best agreement. Distance-dependent analysis further indicates a short-range chemical-enhancement regime below about 4 \u00c5, marked by charge separation, HOMO stabilization, and selective amplification of vibrational modes localized at the molecule\u2013gold adsorption interface. This work introduces a multitautomer modeling strategy that explicitly goes beyond the conventional single-molecule 1:1 adsorption paradigm, demonstrating that only the concurrent treatment of surface coverage, tautomeric coexistence, and short-range charge transfer yields a physically consistent and quantitatively accurate description of the SERS response.<\/jats:p>","DOI":"10.1021\/acs.jpcc.6c03520","type":"journal-article","created":{"date-parts":[[2026,9,27]],"date-time":"2026-09-27T15:01:33Z","timestamp":1790521293000},"page":"13824-13841","source":"Crossref","is-referenced-by-count":0,"title":["Molecular Modeling\nof the Raman and SERS Response\nof 6-Mercaptopurine: Tautomerism, Surface Coverage, and Charge\nTransfer"],"prefix":"10.1021","volume":"130","author":[{"ORCID":"https:\/\/orcid.org\/0009-0009-2502-4889","authenticated-orcid":true,"given":"Paola","family":"Cimino","sequence":"first","affiliation":[{"name":"University of Napoli Federico II , , Complesso Universitario di Monte S. Angelo, via Cintia 21 , ,","place":["Napoli, Italy, I-80126"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pellegrino","family":"Musto","sequence":"additional","affiliation":[{"name":"Institute for Polymers, Composites and Biomaterials, National Research Council of Italy , Via Campi Flegrei, 34 , , ,","place":["Pozzuoli, NA, Italy, 80078"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marianna","family":"Pannico","sequence":"additional","affiliation":[{"name":"Institute for Polymers, Composites and Biomaterials, National Research Council of Italy , Via Campi Flegrei, 34 , , ,","place":["Pozzuoli, NA, Italy, 80078"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5845-4211","authenticated-orcid":true,"given":"Federico","family":"Coppola","sequence":"additional","affiliation":[{"name":"Scuola Superiore Meridionale , Via Mezzocannone 4 , ,","place":["Napoli, Italy, I-80134"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2983-766X","authenticated-orcid":true,"given":"Nadia","family":"Rega","sequence":"additional","affiliation":[{"name":"Scuola Superiore Meridionale , Via Mezzocannone 4 , ,","place":["Napoli, Italy, I-80134"]},{"name":"Istituto Nazionale Di Fisica Nucleare, Sezione di Napoli , Complesso Universitario di Monte S. 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