{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,7,30]],"date-time":"2025-07-30T11:20:12Z","timestamp":1753874412200,"version":"3.41.2"},"reference-count":30,"publisher":"AIP Publishing","issue":"18","funder":[{"name":"NASA Emerging Worlds","award":["80NSSC18K0584"],"award-info":[{"award-number":["80NSSC18K0584"]}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["AST-1907910"],"award-info":[{"award-number":["AST-1907910"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2022,11,14]]},"abstract":"<jats:p>The millimeter\/submillimeter-wave spectrum of the SiP radical (X2\u03a0i) has been recorded using direct absorption spectroscopy in the frequency range of 151\u2013532\u00a0GHz. SiP was synthesized in an AC discharge from the reaction of SiH4 and gas-phase phosphorus, in argon carrier gas. Both spin\u2013orbit ladders were observed. Fifteen rotational transitions were measured originating in the \u03a9 = 3\/2 ladder, and twelve in the \u03a9 = 1\/2 substate, each exhibiting lambda doubling and, at lower frequencies, hyperfine interactions from the phosphorus nuclear spin of I = 1\/2. The lambda-doublets in the \u03a9 = 1\/2 levels appeared to be perturbed at higher J, with the f component deviating from the predicted pattern, likely due to interactions with the nearby excited A2\u03a3+ electronic state, where \u0394E\u03a0-\u03a3 \u223c 430\u00a0cm\u22121. The data were analyzed using a Hund\u2019s case a\u03b2 Hamiltonian and rotational, spin\u2013orbit, lambda-doubling, and hyperfine parameters were determined. A 2\u03a0\/2\u03a3 deperturbation analysis was also performed, considering spin\u2013orbit, spin-electronic, and L-uncoupling interactions. Although SiP is clearly not a hydride, the deperturbed parameters derived suggest that the pure precession hypothesis may be useful in assessing the 2\u03a0\/2\u03a3 interaction. Interpretation of the Fermi contact term, bF, the spin-dipolar constant, c, and the nuclear spin-orbital parameter, a, indicates that the orbital of the unpaired electron is chiefly p\u03c0 in character. The bond length in the v = 0 level was found to be r0 = 2.076 \u00c5, suggestive of a double bond between the silicon and phosphorus atoms.<\/jats:p>","DOI":"10.1063\/5.0118939","type":"journal-article","created":{"date-parts":[[2022,11,10]],"date-time":"2022-11-10T12:57:30Z","timestamp":1668085050000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":2,"title":["The millimeter-wave spectrum of the SiP radical (X2\u03a0i): Rotational perturbations and hyperfine structure"],"prefix":"10.1063","volume":"157","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7788-739X","authenticated-orcid":false,"given":"M. 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