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The excited state dynamics in the trans-dithionated PDI (S2-PDI) are studied here. Unlike PDI, the photo absorbing \u03c0\u03c0* state of S2-PDI is in close proximity to quasi-degenerate n\u03c0* states. The latter exhibits an interesting vibronic problem leading to the breaking of orbital symmetry mediated through non-totally symmetric vibrations. The time-dependent quantum dynamics are studied with a diabatic model Hamiltonian involving three singlet and three triplet states coupled via 22 vibrational modes. A combined effect of multiple internal-conversion and inter-system crossing (ISC) pathways leads to population transfer from the 1\u03c0\u03c0* state to the 3\u03c0\u03c0* state via the n\u03c0* states, with an overall ISC rate of 0.70\u00a0ps that compares well with the experimental value. The calculated absorption spectra for PDI and S2-PDI reproduce the essential vibronic features in the observed experimental spectra. The dominant vibronic progressions are found to have significant contributions from the vinyl stretching modes of the PDI core.<\/jats:p>","DOI":"10.1063\/5.0167127","type":"journal-article","created":{"date-parts":[[2023,9,15]],"date-time":"2023-09-15T12:42:58Z","timestamp":1694781778000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["The interplay of vibronic and spin\u2013orbit coupling in the fluorescence quenching in <i>trans<\/i>-dithionated PDI"],"prefix":"10.1063","volume":"159","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3024-612X","authenticated-orcid":false,"given":"Kishan Kumar","family":"Dakua","sequence":"first","affiliation":[{"name":"Department of Chemistry, Indian Institute of Technology Kharagpur 1 , Kharagpur, India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9255-477X","authenticated-orcid":false,"given":"Karunamoy","family":"Rajak","sequence":"additional","affiliation":[{"name":"Centre for Theoretical Studies, Indian Institute of Technology Kharagpur 2 , Kharagpur, India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2551-1021","authenticated-orcid":false,"given":"Sabyashachi","family":"Mishra","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Indian Institute of Technology Kharagpur 1 , Kharagpur, India"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2023,9,15]]},"reference":[{"key":"2023091512413772500_c1","doi-asserted-by":"publisher","first-page":"160","DOI":"10.1016\/j.dyepig.2013.01.020","volume":"98","year":"2013","journal-title":"Dyes Pigm."},{"key":"2023091512413772500_c2","doi-asserted-by":"publisher","first-page":"3947","DOI":"10.1002\/adfm.200800943","volume":"18","year":"2008","journal-title":"Adv. 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