{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,16]],"date-time":"2026-03-16T13:16:57Z","timestamp":1773667017323,"version":"3.50.1"},"reference-count":65,"publisher":"Wiley","issue":"5","license":[{"start":{"date-parts":[[2010,3,11]],"date-time":"2010-03-11T00:00:00Z","timestamp":1268265600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Magnetic Reson in Chemistry"],"published-print":{"date-parts":[[2010,5]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>An explicit DFT modeling of water surroundings on the electron paramagnetic resonance properties of 4\u2010amino\u20102,2,6,6\u2010tetramethyl\u2010piperidine\u2010<jats:italic>N<\/jats:italic>\u2010oxyl (TA) has been performed. A stepwise hydration of TA is accompanied with certain changes in geometrical parameters (bond lengths and angles) and redistribution of partial electric charges in TA. An aqueous cluster of 45 water molecules can be considered as an appropriate model for a complete aqueous shell around TA, although most of the structural and electronic characteristics of TA already converge at about 10 water molecules. Water surroundings induce an increase in electron spin density on the nitrogen atom of the nitroxide fragment due to stabilization of the polar resonance structure &gt; N<jats:sup>+\u2022<\/jats:sup>\uf8ffO<jats:sup>\u2212<\/jats:sup> at the expense of less polar structure &gt; N\uf8ffO<jats:sup>\u2022<\/jats:sup>. The water\u2010induced rise of the isotropic splitting constant <jats:italic>a<\/jats:italic><jats:sub>iso<\/jats:sub>, calculated from the contact term of the hyperfine interaction, comprises \u0394<jats:italic>a<\/jats:italic><jats:sub>iso<\/jats:sub>(\u03c1<jats:sub>N2<\/jats:sub>) = 2.2\u20132.5 G, which is typical of experimental value for TA. There are two contributions to the solvent effect on the <jats:italic>a<\/jats:italic><jats:sub>iso<\/jats:sub>(\u03c1<jats:sub>N2<\/jats:sub>) value: the redistribution of spin density in the nitroxide fragment (polarity effect) and water\u2010induced distortions of TA geometry. Microscopic variations in a hydrogen\u2010bonded water network cause noticeable fluctuations of the splitting constant <jats:italic>a<\/jats:italic><jats:sub>iso<\/jats:sub>(\u03c1<jats:sub>N2<\/jats:sub>). Calculations of the atomic spin density (\u03c3<jats:sub>N2<\/jats:sub>) allowed us to compute the splitting constant from the relationship <jats:italic>a<\/jats:italic><jats:sub>iso<\/jats:sub>(\u03c3<jats:sub>N2<\/jats:sub>) = <jats:italic>Q<\/jats:italic>\u03c3<jats:sub>N2<\/jats:sub>, where <jats:italic>Q<\/jats:italic> = 36.2 G. A practical advantage of using this relationship is that it gives \u2018smoothed\u2019 values of the splitting constant, which are sensitive to the environment polarity but remain tolerant to microscopic fluctuations of the hydrogen\u2010bonded water network around a spin\u2010label molecule. Copyright \u00a9 2010 John Wiley &amp; Sons, Ltd.<\/jats:p>","DOI":"10.1002\/mrc.2585","type":"journal-article","created":{"date-parts":[[2010,3,11]],"date-time":"2010-03-11T05:13:03Z","timestamp":1268284383000},"page":"337-349","source":"Crossref","is-referenced-by-count":19,"title":["DFT study of nitroxide radicals: explicit modeling of solvent effects on the structural and electronic characteristics of 4\u2010amino\u20102,2,6,6\u2010tetramethyl\u2010piperidine\u2010<i>N<\/i>\u2010oxyl"],"prefix":"10.1002","volume":"48","author":[{"given":"Larissa N.","family":"Ikryannikova","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Leila Yu.","family":"Ustynyuk","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Alexander N.","family":"Tikhonov","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2010,3,11]]},"reference":[{"key":"e_1_2_1_2_2","volume-title":"Spin Labeling: Theory and Applications","author":"Berliner L. 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