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We focus on the effect of excitation energy on the subsequent dynamics. The absorption spectrum of o-nitrophenol has two peaks, centered at 3.9\u00a0eV (\u223c320\u00a0nm) and 5.1\u00a0eV (\u223c240\u00a0nm), and we performed dynamics starting from each of these peaks. The results show that even though the relaxation time constants are similar for the two excitation windows, the underlying dynamics are different. When exciting to the low energy peak, the dynamics are dominated by intramolecular proton transfer followed by internal conversion to the ground state, while exciting to the high-energy peak leads to fast internal conversion to the first excited state and slower decay to the ground state. In this case, intramolecular proton transfer does not occur as frequently, and many trajectories decay to the ground state through conical intersections without proton transfer. By calculating spin\u2013orbit coupling values along the trajectories, we also show that intersystem crossing is possible. Based on the Landau\u2013Zener probability formula, we estimate that there is about a 30%\u201340% probability that intersystem crossing will occur within 1\u00a0ps.<\/jats:p>","DOI":"10.1063\/5.0274633","type":"journal-article","created":{"date-parts":[[2025,7,9]],"date-time":"2025-07-09T11:51:23Z","timestamp":1752061883000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":4,"title":["How excitation wavelength affects excited state dynamics in <i>o<\/i>-nitrophenol: A theoretical perspective"],"prefix":"10.1063","volume":"163","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8994-8209","authenticated-orcid":false,"given":"Dakshitha","family":"Abeygunewardane","sequence":"first","affiliation":[{"name":"Department of Chemistry, Temple University 1 , Philadelphia, Pennsylvania 19122,","place":["USA"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9343-7276","authenticated-orcid":false,"given":"Thomas","family":"Weinacht","sequence":"additional","affiliation":[{"name":"Physics Department, Stony Brook University 2 , Stony Brook, New York 11790,","place":["USA"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2773-3979","authenticated-orcid":false,"given":"Spiridoula","family":"Matsika","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Temple University 1 , Philadelphia, Pennsylvania 19122,","place":["USA"]}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2025,7,9]]},"reference":[{"key":"2025070907511910200_c1","doi-asserted-by":"publisher","first-page":"2028","DOI":"10.1039\/b516590c","article-title":"The photolysis of ortho-nitrophenols: A new gas phase source of HONO","volume":"8","year":"2006","journal-title":"Phys. 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