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The new molecular spin Hamiltonian contains a novel spin\u2013vibrational orbit interaction with a non-adiabatic origin, together with the traditional molecular Zeeman and zero-field splitting interactions with an adiabatic origin. The spin\u2013vibrational orbit interaction represents a non-Abelian Berry curvature on the ground-state electronic manifold and corresponds to an effective magnetic field in the electronic spin dynamics. We further develop a spin relaxation rate model that estimates the spin relaxation time via the two-phonon Raman process. An application of the extended molecular spin Hamiltonian together with the spin relaxation rate model to Cu(II) porphyrin, a prototypical S = 1\/2 molecular qubit, demonstrates that the spin relaxation time at elevated temperatures is dominated by the non-adiabatic spin\u2013vibrational orbit interaction. The computed spin relaxation rate and its magnetic field orientation dependence are in excellent agreement with experimental measurements.<\/jats:p>","DOI":"10.1063\/5.0198519","type":"journal-article","created":{"date-parts":[[2024,4,23]],"date-time":"2024-04-23T07:50:48Z","timestamp":1713858648000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":16,"title":["A novel non-adiabatic spin relaxation mechanism in molecular qubits"],"prefix":"10.1063","volume":"160","author":[{"ORCID":"https:\/\/orcid.org\/0009-0000-6989-7416","authenticated-orcid":false,"given":"Philip","family":"Shushkov","sequence":"first","affiliation":[{"name":"Department of Chemistry, Indiana University , Bloomington, Indiana 47405, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2024,4,23]]},"reference":[{"key":"2024042311504228000_c1","doi-asserted-by":"publisher","first-page":"301","DOI":"10.1038\/s41557-019-0232-y","article-title":"Molecular spins for quantum computation","volume":"11","year":"2019","journal-title":"Nat. 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