{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,13]],"date-time":"2025-11-13T12:48:19Z","timestamp":1763038099848,"version":"3.41.2"},"reference-count":54,"publisher":"AIP Publishing","issue":"14","funder":[{"DOI":"10.13039\/501100001843","name":"Science and Engineering Research Board","doi-asserted-by":"publisher","award":["CRG\/2021\/006050","CRG\/2022\/001425"],"award-info":[{"award-number":["CRG\/2021\/006050","CRG\/2022\/001425"]}],"id":[{"id":"10.13039\/501100001843","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2025,4,14]]},"abstract":"<jats:p>The structure of the first five singlet excited electronic states of meta-nitrophenolate (m-NP) and para-nitrophenolate (p-NP) is investigated here in the gas phase, micro-solvent, and bulk solvent environments. The first excited state (S1) of m-NP was found to be a charge transfer state in the gas phase, whereas that of p-NP is a \u03c0\u03c0* state. A stronger coupling between the donor and acceptor molecular orbitals in p-NP leads to a higher excitation energy of the S1 state as compared to m-NP. An examination of the topography of the potential energy surfaces reveals low energy conical intersections of the S1 state with the S2 and S3 states in p-NP. Such conical intersections in m-NP are located at higher energies relative to the S1 state minimum. Repulsion between the S1(1A\u2032) and S2(1A\u2033) electronic states via the out-of-plane \u2013NO2 torsional mode leads to a symmetrical double well topography of the S1 state of m-NP. Present results establish that while a single solvent molecule like water, methanol, and acetonitrile leads to a blue shift in the first absorption band maxima of m-NP, the electronic localization on the donor molecular orbital due to a single water molecule yields a red shift in the first absorption band of p-NP. However, the attachment of a single water molecule to the nitro site of p-NP facilitates electronic delocalization, leading to a blue shift in the S1 state excitation energy. As a result, in an aqueous medium, the first absorption band maximum was observed very near to that found in bare p-NP.<\/jats:p>","DOI":"10.1063\/5.0249627","type":"journal-article","created":{"date-parts":[[2025,4,11]],"date-time":"2025-04-11T10:42:54Z","timestamp":1744368174000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":3,"title":["Photophysics of <i>meta<\/i>- and <i>para<\/i>-nitrophenolate. I. The role of configuration, microsolvation, and solvation on the charge transfer transition"],"prefix":"10.1063","volume":"162","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3060-795X","authenticated-orcid":false,"given":"Tanmoy","family":"Mondal","sequence":"first","affiliation":[{"name":"Department of Chemistry, Koneru Lakshmaiah Education Foundation 1 , Hyderabad 500 075,","place":["India"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4301-9663","authenticated-orcid":false,"given":"Arun Kumar","family":"Kanakati","sequence":"additional","affiliation":[{"name":"School of Chemistry, University of Hyderabad 2 , Hyderabad 500 046,","place":["India"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2075-6353","authenticated-orcid":false,"given":"S.","family":"Mahapatra","sequence":"additional","affiliation":[{"name":"School of Chemistry, University of Hyderabad 2 , Hyderabad 500 046,","place":["India"]}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2025,4,11]]},"reference":[{"key":"2025041106413037800_c1","doi-asserted-by":"publisher","first-page":"4971","DOI":"10.1021\/cr040084k","volume":"104","year":"2004","journal-title":"Chem. 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