Nitranilic acid hexahydrate, a novel benchmark system of the Zundel cation in an intrinsically asymmetric environment: spectroscopic features and hydrogen bond dynamics characterised by experimental and theoretical methods

Molčanov, Krešimir; Stare, Jernej; Vener, Mikhail; Kojić-Prodić, Biserka; Mali, Gregor; Grdadolnik, Jože; Mohaček Grošev, Vlasta (2014) Nitranilic acid hexahydrate, a novel benchmark system of the Zundel cation in an intrinsically asymmetric environment: spectroscopic features and hydrogen bond dynamics characterised by experimental and theoretical methods. Physical Chemistry Chemical Physics, 16 (3). pp. 998-1007. ISSN 1463-9076

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Abstract

Nitranilic acid (2, 5-dihydroxy-3, 6-dinitro-2, 5- cyclohexadiene-1, 4-dione) as a strong dibasic acid in acidic aqueous media creates the Zundel cation, H5O2+. The structural unit in a crystal comprises (H5O2)2+ (2, 5-dihydroxy-3, 6-dinitro-1, 4-benzoquinonate)2- dihydrate where the Zundel cation reveals no symmetry, being an ideal case for studying proton dynamics and its stability. The Zundel cation and proton transfer dynamics are studied by variable-temperature X-ray diffraction, IR and solid-state NMR spectroscopy, and various quantum chemical methods, including periodic DFT calculations, ab initio molecular dynamics simulation, and quantization of nuclear motion along three fully coupled internal coordinates. The Zundel cation features a short H-bond with the O∙∙∙O distance of 2.433(2) Å with an asymmetric placement of hydrogen. The proton potential is of a single well type and, due to the non-symmetric surroundings, of asymmetric shape. The formation of the Zundel cation is facilitated by the electronegative NO2 groups. The employed spectroscopic techniques supported by calculations confirm a presence of a short H-bond with a complex proton dynamics.

Item Type:	Article
Uncontrolled Keywords:	Zundel cation, proton transfer, hydronuim ion, strong hydrogen bond, variable-temperature X-ray diffraction, IR spectroscopy, solid-state NMR, quantum chemistry, periodic DFT calculations, molecular dynamics simulation, quantization of nuclear motion
Subjects:	NATURAL SCIENCES > Physics NATURAL SCIENCES > Chemistry
Divisions:	Division of Materials Physics Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Fizika i primjena nanostruktura i volumne tvari [135746] Mile Ivanda 098-0982904-2898 MZOS Protein-ligand međudjelovanja na atomnoj razini [77430] Marija Luić 098-1191344-2943 MZOS
Depositing User:	Vlasta Mohaček Grošev
Date Deposited:	08 Jan 2014 12:25
URI:	http://fulir.irb.hr/id/eprint/1243
DOI:	10.1039/C3CP54026J

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