Low-Lying Electronic States in Bismuth Trimer Bi3 as Revealed by Laser Induced NIR Emission Spectroscopy in Solid Ne
Low-Lying Electronic States in Bismuth Trimer Bi3 as Revealed by Laser Induced NIR Emission Spectroscopy in Solid Ne
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固体氖中激光诱导近红外发射光谱揭示铋三聚体 Bi3 中的低电子态
DOI：
10.1021/jp509714f
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
K.Kawaguchi
中科院分区：
文献类型：
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作者：
T.Wakabayashi;Y.Wada;K.Nakajima;Y.Morisawa;S.Kuma;Y.Miyamoto;N.Sasao;M.Yoshimura;T.Sato;K.Kawaguchi
在870-1670 nm范围内记录了3 K下嵌入固体氖基质中的中性铋定时器Bi 3的激光诱导近红外（NIR）发射光谱。使用低能量光子在1064 nm处的光激发，两个发射带系统被新确定的原始带atT 0 = 6600和8470 cm-1。据此，对最近报道的三个近红外光谱系统的光谱归属进行了部分修正，并对T0 = 9625和11395 cm-1的光谱进行了重新确认。铋三聚体（Bi 3）基态电子能级对之间的自旋-轨道耦合导致的能量分裂为1870 ± 1.5 cm-1，这两个能级都具有频率为ωe″= 150 cm-1的全对称振动模式。这对电子激发态的跃迁分别位于基态上方T0 = 8470和9625 cm-1处，自旋轨道耦合距离为1155 cm-1，具有较长的衰减常数，分别为τ = 0.2和τ = 0.1 ms。
Laser-induced near-infrared (NIR) emission spectra of neutral bismuth timer, Bi3, embedded in solid neon matrixes at 3 K were recorded in a range 870–1670 nm. Using photoexcitation with low energy photons at 1064 nm, two emission band systems were newly identified by their origin bands atT0= 6600 and 8470 cm–1. Accordingly, spectral assignment for three NIR emission band systems reported recently was partly revised for the one with its origin band atT0= 7755 cm–1and reconfirmed for the others atT0= 9625 and 11 395 cm–1. Energy splitting by spin–orbit coupling between the pair of electronic energy levels in the ground state of bismuth trimer, Bi3, both having a totally symmetric vibrational mode of frequency at ωe″= 150 cm–1, was determined to be 1870 ± 1.5 cm–1. Transitions from the pair of electronically excited states, locating atT0= 8470 and 9625 cm–1above the ground state and separated by spin–orbit coupling of 1155 cm–1, have relatively long decay constants of τ ∼0.2 and ∼0.1 ms, respectively.