An ab initio and Raman investigation of sulfate ion hydration

Journal of Physical Chemistry A

Volumn 105, Issue 5, 2001, Pages 905-912

  Pye, Cory C ^a   Rudolph, Wolfram W ^b  

^a SAINT MARY S UNIVERSITY   (Canada)

^b DRESDEN UNIVERSITY OF TECHNOLOGY   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

HYDRATION; IONS; ISOMERS; NUMERICAL METHODS; RAMAN SPECTROSCOPY; SULFUR COMPOUNDS;

AMMONIUM SULFATE; BASIS SET SUPERPOSITION ERROR; VIBRATIONAL FREQUENCIES;

AMMONIUM COMPOUNDS;

EID: 0035250604     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp003253n     Document Type: Article

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33. We would like to thank an anonymous referee (B) for reminding us that a negative sign of the orbital energy is not a sufficient condition for proving the stability of a dianion, due to the use of a restricted Hartree-Fock wave function and subsequent perturbation treatments. We dealt with this problem in the following way. For each given stoichiometry, we selected the most stable doubly charged species. With the optimized geometry at each corresponding restricted level, we performed a single-point calculation on the singly charged radical anion using Gaussian 98 (Rev. A.9, Frisch, M. J. et al., Gaussian, Inc., Pittsburgh, PA 1998) at the unrestricted level, including spin projection for the MP2 calculations (as UHF/B, UMP2/B, and PMP2/B, and for the smallest two clusters, with basis set C). Initial guess orbitals were taken from the doubly charged ion because the default guess resulted in convergence to a different state of higher energy. Energy differences between the two versions of Gaussian for the dianion were less than 0.0001 au. The single point calculation should suffice because the SOMO is a nonbonding orbital. The results are given in Table S20. The resulting wave functions had moderate spin contamination (S2 about 0.85 versus 0.75 expected for a doublet) which upon projection stabilized the structures by about 25 kJ/mol. The sulfate dianion is preferentially stabilized by water, in accord with a simple Born model for a more highly charged ion, but in the gas phase is unstable with respect to electron loss (by 90-150 kJ/mol). For the monohydrate, UHF theory predicts a strong preference for the singly charged ion (85 kJ/mol) whereas UMP2 theory predicts only a slight preference (7 kJ/mol). For the dihydrate, UHF predicts a strong preference for the dianion (51 kJ/mol), whereas UMP2 theory predicts only a slight preference (1 kJ/mol). The dianion is preferred for structures with more than two waters.
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