Spectroscopy of Jet-Cooled Bi₃

Abstract

A resonant two-photon ionization spectroscopic study of jet-cooled Bi3 has identified two band systems in the molecule in the 9600-10 600 and 15 250-16 050 cm(-1) range. The latter of these has been previously observed in matrix isolation spectroscopy and tentatively attributed to Bi4; the mass-resolved work presented here reassigns it to Bi3. A review of all previously observed electronic states is presented, and it is argued that the new band system lying in the range 9600-10 600 cm(-1) corresponds to the spin-forbidden A' 4A1" <-- X1 2E" (E1/2 component) band system.

Low-Lying Electronic States in Bismuth Trimer Bi3 As Revealed by Laser-Induced NIR Emission Spectroscopy in Solid Ne

“…In the following sections, we revise our previous argument by showing evidence for the presence of another low-lying electronic state locating above the ground state by ∼1870 cm –1 . The new assignment provides better consistency with the preceding experiments by photoelectron spectroscopy and resonant two-photon ionization spectroscopy, both combined with mass-selective detection of bismuth trimer in the gas phase.…”

“…31 The series of bands following the origin band at 9626.3 cm −1 with a peculiar vibrational progression of 130.0 cm −1 in the upper electronic state corresponds to the absorption spectrum for the electronic transitions in β system. The band origin at 9625 cm −1 in solid Ne is in good agreement with that at 9626.3 cm −1 in the gas phase, consistent with the assignment of the carrier to the trimer, Bi 3 .…”

“…Table 3 summarizes these correspondences together with symmetry assignments from the molecular orbital considerations for a triangular form. 31 An early LIF study of Bi n species trapped in solid Ar reported a ground state vibrational frequency of ω e ″ ∼ 150 cm −1 that was attributed to Bi 2 . 24 Subsequent studies, conducted in Ne and Ar matrixes, found a vibrational frequency of 173 cm −1 for Bi 2 , in agreement with the gas phase value.…”

“…Bismuth is a heavy element of semimetallic properties in its solid form. Molecular bismuth, Bi n ( n = 2–4), exists in its vapor phase, as investigated by trapping molecules in rare-gas matrixes. − Arrington and Morse observed recently vibronic systems in triatomic bismuth, Bi 3 , in the near-infrared (NIR) region by resonant two-photon ionization (R2PI) spectroscopy in the gas phase, locating their origin bands at 9626 and 9673 cm –1 . Very recently, NIR emission band systems were newly found for small bismuth molecules in solid neon matrixes upon excitation with 692 nm photons .…”

Structure and dynamics in liquid bismuth and Bin clusters: A density functional study

“…16,17 Bi + n cations 18 have been identified mass spectroscopically to n > 40, and photofragmentation of small Bi cluster cations has been observed. 19,20 In addition to measurements on Bi 2 and Bi 4 (in solid Ne and Ar matrices), 21 on anions Bi − 2 , Bi − 3 , and Bi − 4 , 22 and on jet-cooled Bi 3 , 23 it has been found that neutral Bi n clusters up to n = 20 show paramagnetic deflections in Stern-Gerlach experiments for odd n. 24 Simulations of liquid pnictogens include work on As, Sb, and Bi by Hafner and Jank, 25 who performed molecular dynamics on samples with up to 2000 atoms using an effective pair potential. They showed that the open structures could be interpreted as a modulation of random packing by oscillations in the effective potentials.…”