{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,20]],"date-time":"2026-08-20T16:27:32Z","timestamp":1787243252415,"version":"build-2736575974"},"reference-count":121,"publisher":"AIP Publishing","issue":"7","content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2026,8,21]]},"abstract":"<jats:p>The current computational study, mostly based on the Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) method, investigates two experimentally well-studied azobenzene-based photoswitches. The study highlights the differences in the photo-isomerization pathways of the 9-membered and 8-membered 2,2\u2032-linked heteroatom-bridged cyclic azobenzene (AZB) systems, designated as R-AZB\u2013(CH2\u2013X\u2013CH2) and AZB\u2013(CH2\u2013X) (where R = tert-butyl, H and X = S, O), respectively. As we move from the 9-membered to the 8-membered system, the stable ground state isomer switches from trans to cis. In R-AZB\u2013(CH2\u2013X\u2013CH2), the strongly allowed S0\u2013S2 transition from the trans-ground state predominantly populates the S2 state. This subsequently relaxes through the rotational and planar S2 minima. The latter minimum, a possible fluorescent geometry, appears along the N=N stretching mode, and it is connected to the S2\/S1-conical intersection (CI) channel. The relaxation pathway along the S1 surface passes through a minimum and torsional S0\/S1\u2013CI to form the cis-photoproduct. A barrier of 4 kcal\/mol has been detected along this path. In contrast, the forward isomerization of AZB\u2013(CH2\u2013X) initiates through equally allowed S0\u2013S1 and S0\u2013S2 transitions from the cis-ground state. No energy minimum (on the S2 or S1 surface) has been noticed along this cis \u2192 trans isomerization path, and a low barrier (\u223c1 kcal\/mol) path leading to the S0\/S1\u2013CI has been identified. These indicate a comparatively more efficient isomerization pathway in the 8-membered ring system, which is in line with their reported superior photo-switching ability. In both cases, the reverse photo-isomerization pathways are barrierless. These reverse isomerization pathways corresponding to the thermal processes have also been investigated in this study for both these systems.<\/jats:p>","DOI":"10.1063\/5.0343744","type":"journal-article","created":{"date-parts":[[2026,8,20]],"date-time":"2026-08-20T16:06:40Z","timestamp":1787242000000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["A comparative study on the isomerization pathways of heteroatom (S, O)-bridged 9-membered and 8-membered cyclic azobenzene photoswitches"],"prefix":"10.1063","volume":"165","author":[{"ORCID":"https:\/\/orcid.org\/0009-0006-5470-4064","authenticated-orcid":false,"given":"Anisha","family":"Mishra","sequence":"first","affiliation":[{"name":"Department of Chemistry, Birla Institute of Technology and Science (BITS), Pilani, K. K. 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