{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,10]],"date-time":"2026-07-10T04:07:12Z","timestamp":1783656432427,"version":"3.55.0"},"reference-count":33,"publisher":"AIP Publishing","issue":"11","funder":[{"name":"NSF","award":["CHE-2053541"],"award-info":[{"award-number":["CHE-2053541"]}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2023,9,21]]},"abstract":"<jats:p>We report a study on the electronic structure and chemical bonding of the BiB molecule using high-resolution photoelectron imaging of cryogenically cooled BiB\u2212 anion. By eliminating all the vibrational hot bands, we can resolve the complicated detachment transitions due to the open-shell nature of BiB and the strong spin\u2013orbit coupling. The electron affinity of BiB is measured to be 2.010(1) eV. The ground state of BiB\u2212 is determined to be 2\u03a0(3\/2) with a \u03c32\u03c03 valence electron configuration, while the ground state of BiB is found to be 3\u03a3\u2212(0+) with a \u03c32\u03c02 electron configuration. Eight low-lying spin\u2013orbit excited states [3\u03a3\u2212(1), 1\u0394(2), 1\u03a3+(0+), 3\u03a0(2), 3\u03a0(1), 1\u03a0(1)], including two forbidden transitions, [3\u03a0(0\u2212) and 3\u03a0(0+)], are observed for BiB as a result of electron detachment from the \u03c3 and \u03c0 orbitals of BiB\u2212. The angular distribution information from the photoelectron imaging is found to be critical to distinguish detachment transitions from the \u03c3 or \u03c0 orbital for the spectral assignment. This study provides a wealth of information about the low-lying electronic states and spin\u2013orbit coupling of BiB, demonstrating the importance of cryogenic cooling for obtaining well-resolved photoelectron spectra for size-selected clusters produced from a laser vaporization cluster source.<\/jats:p>","DOI":"10.1063\/5.0170325","type":"journal-article","created":{"date-parts":[[2023,9,15]],"date-time":"2023-09-15T12:44:11Z","timestamp":1694781851000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":10,"title":["On the electronic structure and spin\u2013orbit coupling of BiB from photoelectron imaging of cryogenically-cooled BiB\u2212 anion"],"prefix":"10.1063","volume":"159","author":[{"ORCID":"https:\/\/orcid.org\/0009-0009-4952-4466","authenticated-orcid":false,"given":"Han-Wen","family":"Gao","sequence":"first","affiliation":[{"name":"Department of Chemistry, Brown University , Providence, Rhode Island 02912, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0023-1872","authenticated-orcid":false,"given":"Hyun Wook","family":"Choi","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Brown University , Providence, Rhode Island 02912, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-1436-7772","authenticated-orcid":false,"given":"Jie","family":"Hui","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Brown University , Providence, Rhode Island 02912, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8432-4437","authenticated-orcid":false,"given":"Wei-Jia","family":"Chen","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Brown University , Providence, Rhode Island 02912, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1388-6472","authenticated-orcid":false,"given":"G. Stephen","family":"Kocheril","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Brown University , Providence, Rhode Island 02912, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1816-5738","authenticated-orcid":false,"given":"Lai-Sheng","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Brown University , Providence, Rhode Island 02912, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2023,9,15]]},"reference":[{"key":"2023091512414886700_c1","doi-asserted-by":"publisher","first-page":"025901","DOI":"10.1103\/physrevlett.111.025901","volume":"111","year":"2013","journal-title":"Phys. Rev. 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