Abstract
Measured frequencies from pure nitrate liquids have been used to calculate the force constants for the nitrate ion and the M+-NO3 − systems (M+ = Li+, Na+, K+, Rb+, and Cs+) by a matrix successive-approximation method based on perturbation theory in dependent coordinates. The valency force constants Kq for the N-O bonds are increased by comparison with free NO −3 . The N-O bond strengthening is not adequately explained by cation-anion interaction because there is electron-density transfer mainly by the π mechanism within the NO −3 . Correction for the vibrational parameters of the interacting particles confirms the previously demonstrated acid-base mechanism for the cation-anion interaction in liquids containing nitrate.
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 230–234, March–April, 1989.
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Shapoval, V.I., Solov'ev, V.V., Kovalenko, N.F. et al. Effects of alkali-metal cations on nitrate-ion N-O bond force constants in ionic melts. Theor Exp Chem 25, 210–213 (1989). https://doi.org/10.1007/BF01135013
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DOI: https://doi.org/10.1007/BF01135013