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To explain these differences, we investigate the solvent effects on <jats:italic>E<\/jats:italic><jats:sub>HOMO<\/jats:sub> by combining density functional theory and molecular dynamics calculations for four donor molecules with a common backbone moiety. We compare the experimental <jats:italic>E<\/jats:italic><jats:sub>HOMO<\/jats:sub> values to the calculated values obtained from either implicit or first solvation shell theories. We find that the first solvation shell method can capture the <jats:italic>E<\/jats:italic><jats:sub>HOMO<\/jats:sub> variation arising from the functional groups in solution, unlike the implicit method. We further applied the first solvation shell method to other semiconducting organic molecules measured in solutions for different solvents. We find that the <jats:italic>E<\/jats:italic><jats:sub>HOMO<\/jats:sub> obtained using an implicit method is insensitive to solvent choice. The first solvation shell, however, produces <jats:italic>E<\/jats:italic><jats:sub>HOMO<\/jats:sub> values that are sensitive to solvent choices and agrees with published experimental results. The solvent sensitivity arises from a hierarchy of three effects: (1) the solute electronic state within a surrounding dielectric continuum, (2) ambient temperature or solvent atoms changing the solute geometry, and (3) electronic interactions between the solute and solvents. The implicit method, on the other hand, only captures the effect of a dielectric environment. Our findings suggest that <jats:italic>E<\/jats:italic><jats:sub>HOMO<\/jats:sub> obtained by CV measurements should account for the influence of solvent when the results are reported, interpreted, or compared to other molecules.<\/jats:p>","DOI":"10.1002\/jcc.27065","type":"journal-article","created":{"date-parts":[[2023,1,4]],"date-time":"2023-01-04T11:12:29Z","timestamp":1672830749000},"page":"1064-1072","update-policy":"https:\/\/2.zoppoz.workers.dev:443\/https\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["The effect of solvent on determining highest occupied molecular orbital energies of semiconducting organic molecules: Insight from a combined computational approach"],"prefix":"10.1002","volume":"44","author":[{"ORCID":"https:\/\/2.zoppoz.workers.dev:443\/https\/orcid.org\/0000-0003-0768-9704","authenticated-orcid":false,"given":"Aaron","family":"Kramer","sequence":"first","affiliation":[{"name":"Department of Physics University of Texas at Dallas  Richardson Texas USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/2.zoppoz.workers.dev:443\/https\/orcid.org\/0000-0003-3790-4153","authenticated-orcid":false,"given":"Ruth","family":"Pachter","sequence":"additional","affiliation":[{"name":"Air Force Research Laboratory, Materials and Manufacturing Directorate Wright\u2010Patterson Air Force Base  Ohio USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/2.zoppoz.workers.dev:443\/https\/orcid.org\/0000-0002-7821-3001","authenticated-orcid":false,"given":"Julia W. 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