Determination of structure and dynamics of the solvated bisulfide (HS -) ion by ab initio QMCF molecular dynamics
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Author list: Kritayakornupong C., Vchirawongkwin V., Rode B.M.
Publisher: American Chemical Society
Publication year: 2010
Journal: Journal of Physical Chemistry B (Soft Condensed Matter and Biophysical Chemistry) (1520-6106)
Volume number: 114
Issue number: 40
Start page: 12883
End page: 12887
Number of pages: 5
ISSN: 1520-6106
eISSN: 1520-5207
Languages: English-Great Britain (EN-GB)
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Abstract
The hydration structure of the bisulfide (HS-) ion in dilute aqueous solution was characterized by means of an ab initio quantum mechanical charge field (QMCF) molecular dynamics simulation at the Hartree - Fock level employing Dunning double-ζ plus polarization function (DZP) basis sets. An average H - S bond distance of 1.35 Å resulted from the simulation and a hydration shell located at 2.42 Å S HS-···Hw and 3.97 Å HS - distances, respectively. At the sulfur site, the average coordination number is 5.9 ± 1.1, while the value for the hydrogen site is 9.2 ± 1.6. The calculated HHS- - SHS- stretching frequency of 2752 cm-1 obtained from the QMCF MD simulation is in good agreement with that reported from the Raman spectrum (2570 cm-1) only if a scaling factor of 0.89 is applied. The stability of the nondissociated HS- structure is reflected by the force constants of 436.1 and 4.5 N/m determined for the HHS- - SHS- and HHS-···Ow bonds, respectively. A weak structure-making effect of the hydrated HS- ion results from the mean residence times of 1.5 and 2.1 ps of coordinated water molecules at the sulfur and hydrogen sites of the HS- ion, respectively. © 2010 American Chemical Society.
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