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

页码：758 / 762

页数：5

共 29 条

[11] Structure of protonated carbon dioxide clusters: Infrared photodissociation spectroscopy and ab initio calculations [J].

Douberly, G. E. ;

Ricks, A. M. ;

Ticknor, B. W. ;

Duncan, M. A. .

JOURNAL OF PHYSICAL CHEMISTRY A, 2008, 112 (05) :950-959

[12] Infrared spectroscopy to probe structure and dynamics in metal ion-molecule complexes [J].

Duncan, MA .

INTERNATIONAL REVIEWS IN PHYSICAL CHEMISTRY, 2003, 22 (02) :407-435

[13] Detection af H-3(+) in interstellar space [J].

Geballe, TR ;

Oka, T .

NATURE, 1996, 384 (6607) :334-335

[14] Dynamical constraints and nuclear spin caused restrictions in HmDn+ collision systems [J].

Gerlich, D. ;

Windisch, F. ;

Hlavenka, P. ;

Plasil, R. ;

Glosik, J. .

PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES, 2006, 364 (1848) :3007-3034

[15] A STUDY OF THE REACTIONS OF H-3+, H2D+, HD2+, AND D3+ WITH H-2, HD, AND D2 USING A VARIABLE-TEMPERATURE SELECTED ION FLOW TUBE [J].

GILES, K ;

ADAMS, NG ;

SMITH, D .

JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (19) :7645-7650

[16] Spectral signatures of hydrated proton vibrations in water clusters [J].

Headrick, JM ;

Diken, EG ;

Walters, RS ;

Hammer, NI ;

Christie, RA ;

Cui, J ;

Myshakin, EM ;

Duncan, MA ;

Johnson, MA ;

Jordan, KD .

SCIENCE, 2005, 308 (5729) :1765-1769

[17] H3+ + H2 isotopic system at low temperatures: Microcanonical model and experimental study [J].

Hugo, Edouard ;

Asvany, Oskar ;

Schlemmer, Stephan .

JOURNAL OF CHEMICAL PHYSICS, 2009, 130 (16)

[18] EXTENDED AB-INITIO STUDY OF THE VIBRATIONAL DYNAMICS OF H-5(+) AND D-5(+) INCLUDING ALL VIBRATIONAL-MODES [J].

KRAEMER, WP ;

SPIRKO, V ;

BLUDSKY, O .

JOURNAL OF MOLECULAR SPECTROSCOPY, 1994, 164 (02) :500-509

[19] Molecular spectroscopy -: H3+ -: Ion with many talents [J].

McCall, BJ ;

Oka, T .

SCIENCE, 2000, 287 (5460) :1941-1942

[20] Quantum studies of the vibrations in H3O2- and D3O2- -: art. no. 064317 [J].

McCoy, AB ;

Huang, XC ;

Carter, S ;

Bowman, JM .

JOURNAL OF CHEMICAL PHYSICS, 2005, 123 (06)

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