Shared-Proton Mode Lights up the Infrared Spectrum of Fluxional Cations H5+ and D5+

被引:53
作者
Cheng, Timothy C. [3 ]
Bandyopadyay, Biswajit [3 ]
Wang, Yimin [1 ,2 ]
Carter, Stuart [1 ,2 ,4 ]
Braams, Bastiaan J. [1 ,2 ]
Bowman, Joel M. [1 ,2 ]
Duncan, Michael A. [3 ]
机构
[1] Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
[2] Emory Univ, Dept Chem, Atlanta, GA 30322 USA
[3] Univ Georgia, Dept Chem, Athens, GA 30602 USA
[4] Univ Reading, Dept Chem, Reading RG6 2AD, Berks, England
来源
JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2010年 / 1卷 / 04期
基金
美国国家科学基金会;
关键词
RANDOM-WALK; AB-INITIO; SPECTROSCOPY; ION; VIBRATIONS; H-3(+); DYNAMICS;
D O I
10.1021/jz100048v
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
We report experimental and calculated infrared spectra of the highly fluxional cations H-5(+) and D-5(+). These cations have been postulated to exist in the interstellar medium and to play a central role in the deuterium fractionation. The experiments produce these ions in a pulsed discharge supersonic nozzle ion source and utilize, mass-selected photodissociation spectroscopy in the 2000-4500 cm(-1) region. Vibrational bands apparently broadened by rapid predissociation are detected throughout this region for both isotopologues. The calculated spectra make use of an ab initio potential energy surface and a new dipole moment surface and are based on results from fixed node quantum diffusion Monte Carlo and variational vibrational calculations. The successful assignment of the experimental spectra requires a proper treatment of the delocalized anharmonic shared-proton mode and indicates a major breakdown of the harmonic approximation. Several calculated, intense spectral features associated with this mode in the far infrared region could guide future observational searches of these cations.
引用
收藏
页码:758 / 762
页数:5
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