处于vHF = 3能级的N₂-HF复合物的振转光谱。

Rovibrational spectra of the N2-HF complex at the vHF=3 level.

作者信息

Medley Patrick, Yu Zhenhong, Connors Brendan, Klemperer William, Tsang Susy N, Chuang Cheng-Chi

机构信息

Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.

出版信息

J Chem Phys. 2006 Jun 7;124(21):214314. doi: 10.1063/1.2203627.

DOI:10.1063/1.2203627

PMID:16774414

Abstract

We report the analyses of the three intermolecular combination bands of the hydrogen-bonded N2-HF complex at vHF=3, observed by molecular beam intracavity laser induced fluorescence. The origin of the HF intermolecular bending combination band, (3001(1)0)<--(00000), is 11 548.45(3) cm(-1), 328.2 cm(-1) higher than that of the (30000)<--(00000) transition with an origin at 11 220.250(1) cm(-1). The average rotational constant of the (3001(1)0) level is 0.103 63(1) cm(-1), a 4.8% reduction from B(30000)=0.109 21(1) cm(-1). Perturbations are observed as line splittings, increased line widths, and reduced peak intensities of a number of lines of the e and f components of (3001(1)0). In addition, the centrifugal distortion coefficients of both components are large, negative, and different. The N2 intermolecular bend transition (30001(1))<--(00000) has an origin at 11 288.706(1) cm(-1), 68.456(2) cm(-1) above that of the (30000)<--(00000) transition. This is the lowest combination state at v(HF)=3 level. It is unperturbed, yielding B(30001(1))=0.110.10(1) cm(-1). The transition to the intermolecular stretching state, (30100)<--(00000), has an origin at 11 318.858(1) cm(-1) with B(30100)=0.105 84(1) cm(-1). Both the (30100) and (30000) levels show an isolated perturbation at J=4. The Lorentzian component of the line widths, which show considerable variation with soft mode, are GammaL(30000)=490(30) MHz, GammaL(30100)=630(30) MHz, GammaL(3001(1)0)=250(30) MHz, and GammaL(30001(1))=500(50) MHz.

摘要

我们报告了通过分子束腔内激光诱导荧光观测到的在(v_{HF}=3)时氢键结合的(N_2 - HF)复合物的三个分子间组合带的分析结果。(HF)分子间弯曲组合带((3001(1)0)\leftarrow(00000))的起源为(11548.45(3) cm^{-1})，比起源于(11220.250(1) cm^{-1})的((30000)\leftarrow(00000))跃迁高(328.2 cm^{-1})。((3001(1)0))能级的平均转动常数为(0.10363(1) cm^{-1})，比(B(30000)=0.10921(1) cm^{-1})降低了(4.8%)。在((3001(1)0))的(e)和(f)分量的许多谱线中观察到微扰，表现为谱线分裂、线宽增加和峰值强度降低。此外，两个分量的离心畸变系数都很大，为负值且不同。(N_2)分子间弯曲跃迁((30001(1))\leftarrow(00000))的起源为(11288.706(1) cm^{-1})，比((30000)\leftarrow(00000))跃迁高(68.456(2) cm^{-1})。这是(v(HF)=3)能级下最低的组合态。它未受微扰，(B(30001(1)) = 0.11010(1) cm^{-1})。向分子间拉伸态((30100)\leftarrow(00000))的跃迁起源为(11318.858(1) cm^{-1})，(B(30100)=0.10584(1) cm^{-1})。((30100))和((30000))能级在(J = 4)时都显示出孤立的微扰。线宽的洛伦兹分量随软模有相当大的变化，(\Gamma_L(30000)=490(30) MHz)，(\Gamma_L(30100)=630(30) MHz)，(\Gamma_L(3001(1)0)=250(30) MHz)，(\Gamma_L(30001(1))=500(50) MHz)。