Display options
Cite
Sedo G, Doran JL, Leopold KR. Partial proton transfer in the nitric acid trihydrate complex. J Phys Chem A. 2009;113(42):11301-10doi: 10.1021/jp9063033.
Sedo, G., Doran, J. L., & Leopold, K. R. (2009). Partial proton transfer in the nitric acid trihydrate complex. The journal of physical chemistry. A, 113(42), 11301-10. https://doi.org/10.1021/jp9063033
Sedo, Galen, et al. "Partial proton transfer in the nitric acid trihydrate complex." The journal of physical chemistry. A vol. 113,42 (2009): 11301-10. doi: https://doi.org/10.1021/jp9063033
Sedo G, Doran JL, Leopold KR. Partial proton transfer in the nitric acid trihydrate complex. J Phys Chem A. 2009 Oct 22;113(42):11301-10. doi: 10.1021/jp9063033. PMID: 19827854.
Copy Download .nbib Format: NLM
Share it on

J Phys Chem A. 2009 Oct 22;113(42):11301-10. doi: 10.1021/jp9063033.

Partial proton transfer in the nitric acid trihydrate complex.

The journal of physical chemistry. A

Galen Sedo, Jamie L Doran, Kenneth R Leopold

Affiliations

  1. Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.

PMID: 19827854 DOI: 10.1021/jp9063033

Abstract

Four isotopologues of the gas-phase complex HNO(3)-(H(2)O)(3) have been observed by microwave spectroscopy in a supersonic jet. Rotational and nuclear electric quadrupole coupling constants have been obtained and the experimentally derived inertial defect has been used to infer a near-planar geometry for the complex. The data identify the observed species from among several structures predicted by theory, favoring a 10-membered ring geometry with the HNO(3) hydrogen-bonded to the first water, a series of water-water hydrogen bonds, and ring completion with the third water acting as a hydrogen-bond donor to an unprotonated HNO(3) oxygen. This structure corresponds to the lowest energy form predicted computationally in several prior studies as well as in this work using the MP2/6-311++G(2df,2pd) level/basis set. Although its observation does not rigorously establish its status as the lowest energy form, the concurrence between the predicted low-energy conformer and that observed in the ultracold supersonic jet strongly suggests that it is indeed the minimum-energy structure. The a-type spectra show evidence of internal dynamics, likely resulting from large amplitude motion of one or more of the water subunits. This complex represents the third step in the sequential hydration of HNO(3), and both the theoretical structure and experimental (14)N quadrupole coupling constants have been used to track the degree of ionization of the acid as function of hydration number. Based on (14)N quadrupole coupling constants, transfer of the HNO(3) proton to its nearest water molecule is about one-third complete in the trihydrate.

Publication Types