High-resolution infrared spectroscopy of trans- and cis-H(18)ON(18)O: equilibrium structures of the nitrous acid isomers.
High-resolution infrared spectroscopy of trans- and cis-H(18)ON(18)O: equilibrium structures of the nitrous acid isomers.
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反式和顺式 H(18)ON(18)O 的高分辨率红外光谱：亚硝酸异构体的平衡结构。
DOI：
10.1021/jp806286p
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发表时间：
2008
期刊：
影响因子：
--
通讯作者：
P. Chelin
中科院分区：
文献类型：
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作者：
V. Sironneau;J. Orphal;Jean Demaison;P. Chelin
本文首次给出了全(18)O取代亚硝酸、反式和顺式-H(18)在(18)O上的nu_4基带的高分辨光谱和分析。这些基带不受相邻振动能级的干扰，首次被用来测定(18)O上反式和顺式-H(18)的基态和nu_4=1态的精确的转动和离心形变常数，然后用基态转动常数与其他HONO同位素的转动常数和从从头计算得到的转动振动参数相结合。准确测定反式和顺式HONO的半实验平衡结构。我们的研究证实了Demaison等人最近的一项研究结果。(J.Phys.化学。A2006110,13609-13617)，而本文得到的顺式HONO的新结构与Cox等人以前的工作相比是一个重大的改进。(J.Mol.结构。1994、320、91-106)。推荐的顺-HONO平衡结构参数为：角(E)(ONO)=113.18(1)度，角(E)(ONO)=104.67(4)度，r(E)(ON)=1.1816(10)A，r(E)(N-O)=1.3887(10)A，r(E)(O-H)=0.9744(7)A。
In this paper, we present the first high-resolution spectra and analysis of the nu 4 fundamental bands of fully (18)O-substituted nitrous acid, trans- and cis-H(18)ON(18)O. These bands are not perturbed by neighboring vibrational levels and were used to determine for the first time accurate rotational and centrifugal distortion constants of the ground and nu 4 = 1 states of trans- and cis-H(18)ON(18)O. The ground-state rotational constants were then used, together with the rotational constants of other HONO isotopic species and with rotation-vibration parameters from ab initio calculations, to determine accurate semi-experimental equilibrium structures of trans- and cis-HONO. Our study confirms the results of a recent work by Demaison et al. (J. Phys. Chem. A 2006, 110, 13609-13617) concerning the structure of trans-HONO, whereas the new structure of cis-HONO obtained in this paper is a significant improvement compared with the previous work of Cox et al. (J. Mol. Struct. 1994, 320, 91-106). The recommended parameters for the equilibrium structure of cis-HONO are r(e)(ON) = 1.1816(10) A, r(e)(N-O) = 1.3887(10) A, r(e)(O-H) = 0.9744(7) A, angle(e)(ONO) = 113.18(1) degrees, and angle(e)(HON) = 104.67(4) degrees.