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Volumn 107, Issue 30, 2003, Pages 5778-5788

Theoretical characterization of oxoanion, XOmn-, solvation

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRODES; HYDROGEN BONDS; NITRATES; QUANTUM THEORY; SOLVENTS; THERMODYNAMIC PROPERTIES;

EID: 0042197595     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0343537     Document Type: Article
Times cited : (38)

References (98)
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    • note
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    • note
    • 75 on terminal oxygens calculated by the SM5 module of HONDO 2002 are typically smaller than the electrostatic potential-derived charges (e.g., 40% smaller in the case of the nitrate ion). However, using these charges in eq 1 makes the oxygen radius in the nitrate ion just 0.06 Å larger, and we find that reducing the nitrogen radius by just 0.07 Å regains agreement of the calculated solvation energy with experiment. Therefore, we conclude that the unique characteristics of our protocol are a result of relating cavity radii to atomic charges and not the charge scheme used for deriving the atomic charges.
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    • note
    • 3 reproduces approximately the electrostatic solvation free energy of the nitrate ion in water. This contour is ∼1.6 Å from N above the molecular plane and ∼1.6 Å from O in the molecular plane compared to 2.4 and 1.52 Å, respectively, by our fitting procedure (Table 1). This contour is also less than ∼1.7 Å from N to the nearest critical points in the region above the molecular plane.


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