Dehghany M, Afshari Mahin, Moazzen-Ahmadi N, McKellar A R W
Department of Physics and Astronomy, University of Calgary, 2500 University Drive North West, Calgary, Alberta T2N 1N4, Canada.
J Chem Phys. 2009 Jan 28;130(4):044303. doi: 10.1063/1.3062957.
Infrared spectra of N(2)O trimers are studied using a tunable diode laser to probe a pulsed supersonic slit-jet expansion. A previous observation by Miller and Pedersen [J. Chem. Phys. 108, 436 (1998)] in the N(2)O nu(1)+nu(3) combination band region ( approximately 3480 cm(-1)) showed the trimer structure to be noncyclic, with three inequivalent N(2)O monomer units which could be thought of as an N(2)O dimer (slipped antiparallel configuration) plus a third monomer unit lying above the dimer plane. The present observations cover the N(2)O fundamental band regions nu(3) ( approximately 1280 cm(-1)) and nu(1) ( approximately 2230 cm(-1)). In the nu(3) region, two trimer bands are assigned with vibrational shifts and other characteristics similar to those in the nu(1)+nu(3) region, but in the nu(1) region all three possible trimer bands are observed. Relationships among the various bands are considered with reference to their rotational intensity patterns, their vibrational shifts, and the properties of the related N(2)O dimer, with results that generally support the conclusions of Miller and Pedersen. Three trimer bands are also observed for the fully (15)N-substituted species in the nu(1) region, and these results should aid in the detection of the as-yet-unobserved pure rotational microwave spectrum of the trimer.
使用可调谐二极管激光器探测脉冲超声速狭缝射流膨胀,研究了N₂O三聚体的红外光谱。米勒和佩德森[《化学物理杂志》108, 436 (1998)]先前在N₂O ν₁+ν₃组合带区域(约3480 cm⁻¹)的观察表明,三聚体结构是非环状的,有三个不等价的N₂O单体单元,可以认为是一个N₂O二聚体(滑移反平行构型)加上位于二聚体平面上方的第三个单体单元。目前的观察覆盖了N₂O基频带区域ν₃(约1280 cm⁻¹)和ν₁(约2230 cm⁻¹)。在ν₃区域,分配了两个三聚体带,其振动位移和其他特征与ν₁+ν₃区域中的相似,但在ν₁区域观察到了所有三个可能的三聚体带。参照其转动强度模式、振动位移以及相关N₂O二聚体的性质,考虑了各个带之间的关系,结果总体上支持了米勒和佩德森的结论。在ν₁区域也观察到了完全¹⁵N取代物种的三个三聚体带,这些结果应该有助于检测尚未观察到的三聚体的纯转动微波光谱。