A theoretical study of the millimeterwave spectrum of CH5+

被引:33
作者
Bunker, PR [1 ]
Ostojic, B [1 ]
Yurchenko, S [1 ]
机构
[1] Natl Res Council Canada, Steacie Inst Mol Sci, Ottawa, ON K1A 0R6, Canada
关键词
theory; protonated methane; high-resolution spectroscopy;
D O I
10.1016/j.molstruc.2003.12.020
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
This is a continuation of our earlier work aimed at predicting the millimeterwave spectrum of protonated methane CH5+. As for protonated acetylene C2H3+, it is the millimeterwave spectrum that will most directly provide the experimental information needed to understand the large amplitude motion of the molecule. Literature ab initio calculations show that the large amplitude motion of the five protons around the central carbon nucleus in CH is not completely free, but is restricted by potential barriers at the trigonal bipyramid (D-3h), square pyramid (C-4v) and end-on-H-2 (C-3v) forms. Thus, the large amplitude motion proceeds mostly in the coordinate space that connects the structures called C-s(I), C-s(II) and C-2v. These structures have essentially identical electronic energies and very similar rotational constants, as has already been shown in the literature. We calculate that they also have very similar dipole moments. The topology of the space of the large amplitude motion that connects the 120 versions of the C-s(I) structure, the 120 versions of the C-s(II) structure, and the 60 versions of the C-2v structure is considered here. The spectral signature of this large amplitude motion in the rotational spectrum is calculated with absolute intensities. It is hoped that these results will aid and stimulate attempts to see and assign the high resolution gas phase millimeterwave absorption spectrum of CH5+. The J = 1 <-- 0 spectrum is predicted to be centered in the region 220-235 GHz, and if all the large amplitude motion splittings of this line are resolved, the strongest component (the K-i = 0 <-- 0 line) is predicted to have an integrated absorption intensity of 13 m/mol at 77 K. (C) 2003 Elsevier B.V. All rights reserved.
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页码:253 / 261
页数:9
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