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Introducing electrostatic models based on minimal distributed charges (MDCM) instead of usual atom\u2010centered point charges (PCs) to realistically describe features such as <jats:italic>\u03c3<\/jats:italic>\u2212holes yields overestimated hydration free energies unless the van der Waals parameters are reparametrized. Scaling van der Waals ranges by 10% to 20% for three Cl\u2010PhOH and most X\u2010Bz yield results within experimental error bars, which is encouraging, whereas for benzene (H\u2010Bz) PC\u2010based models are sufficient. Replacing the bonded terms by a neural network\u2010trained energy function featuring fluctuating atom\u2010centered PCs also yields qualitatively correct hydration free energies, which can be brought into agreement with experiments within error bars after adaptation of the van der Waals parameters. The infrared spectroscopy of Cl\u2010PhOH is rather well captured by all models, although the ML\u2010based energy function performs somewhat better in the region of the framework modes. The present work finds that refinements of empirical energy functions for targeted applications are a meaningful way toward more quantitative and physics\u2010based simulations. At the same time, empirical energy functions have matured to a remarkable degree, at least for the species considered in the present work.<\/jats:p>","DOI":"10.1002\/jcc.70162","type":"journal-article","created":{"date-parts":[[2025,8,2]],"date-time":"2025-08-02T17:09:08Z","timestamp":1754154548000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Enhancing Empirical Energy Functions Using Physics\u2010 and Machine Learning\u2010Based Extensions: Structure, Dynamics and Spectroscopy of Modified Benzenes"],"prefix":"10.1002","volume":"46","author":[{"given":"Kham","family":"Lek Chaton","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Basel  Basel Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7930-8806","authenticated-orcid":false,"given":"Markus","family":"Meuwly","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Basel  Basel Switzerland"},{"name":"Department of Chemistry Brown University  Providence Rhode Island USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,8,2]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1187409"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.27367"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c04169"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcb.4c05480"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp973084f"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00315a051"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/bip.360230807"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00214a001"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/jz501315h"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.540070502"},{"key":"e_1_2_8_12_1","first-page":"2098","article-title":"Predicting Crystal Structures of Organic Compounds","volume":"43","author":"Price S. 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