Infrared Multiple Photon Dissociation Spectroscopy of Sodium and Potassium Chlorate Anions

Journal Article · Fri Jan 01 00:00:00 EST 2010 · Rapid Communications in Mass Spectrometry

DOI:https://doi.org/10.1002/rcm.4379· OSTI ID:983952

Dain, Ryan P; Leavitt, Christopher M; Oomens, Jos; Steill, Jeffrey D; Groenewold, Gary S; van Stipdonk, Michael J

The structures of gas-phase, metal chlorate anions with the formula [M(ClO3)2]-, M=Na and K, were determined using tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. Structural assignments for both anions are based on comparisons of the experimental vibrational spectra for the two species to those predicted by density functional theory and involve conformations that feature either bidentate or tridentate coordination of the cation by chlorate. Our results strongly suggest that a structure in which both chlorate anions are bidentate ligands is preferred for [Na(ClO3)2]-. However, for [K(ClO3)2]- the best agreement between experimental and theoretical spectra is obtained from a composite of predicted spectra for which the chlorate anions are either both bidentate or both tridentate ligands. In general, we find that the overall accuracy of DFT calculations for prediction of IR spectra is dependent on both functional and basis set, with best agreement achieved using frequencies generated at the B3LYP/6-311+g(3df) level of theory.

• Research Organization: Idaho National Lab. (INL), Idaho Falls, ID (United States)
• Sponsoring Organization: DOE - NE
• DOE Contract Number: DE-AC07-05ID14517
• OSTI ID: 983952
• Report Number(s): INL/JOU-09-16449; ISSN 1097-0231; TRN: US1005210
• Journal Information: Rapid Communications in Mass Spectrometry, Vol. 24, Issue 2; ISSN 0951-4198
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACCURACY
ANIONS
CATIONS
CHLORATES
DISSOCIATION
FUNCTIONALS
MASS SPECTROSCOPY
PHOTONS
POTASSIUM
SODIUM
SPECTRA
SPECTROSCOPY
chlorate complexes
computational chemistry
coordination complexes
density functional theory
Infrared spectroscopy
IRMPD
mass spectrometry