Shared-Proton Mode Lights up the Infrared Spectrum of Fluxional Cations H5+ and D5+
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作者:
Cheng, Timothy C.
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Univ Georgia, Dept Chem, Athens, GA 30602 USAEmory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
Cheng, Timothy C.
[3
]
Bandyopadyay, Biswajit
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Univ Georgia, Dept Chem, Athens, GA 30602 USAEmory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
Bandyopadyay, Biswajit
[3
]
Wang, Yimin
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Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
Emory Univ, Dept Chem, Atlanta, GA 30322 USAEmory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
Wang, Yimin
[1
,2
]
Carter, Stuart
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Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
Emory Univ, Dept Chem, Atlanta, GA 30322 USA
Univ Reading, Dept Chem, Reading RG6 2AD, Berks, EnglandEmory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
Carter, Stuart
[1
,2
,4
]
Braams, Bastiaan J.
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Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
Emory Univ, Dept Chem, Atlanta, GA 30322 USAEmory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
Braams, Bastiaan J.
[1
,2
]
Bowman, Joel M.
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Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
Emory Univ, Dept Chem, Atlanta, GA 30322 USAEmory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
Bowman, Joel M.
[1
,2
]
Duncan, Michael A.
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Univ Georgia, Dept Chem, Athens, GA 30602 USAEmory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
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
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.