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High-resolution electron spin resonance spectroscopy of XeF center dot in solid argon. The hyperfine structure constants as a probe of relativistic effects in the chemical bonding properties of a heavy noble gas atomстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
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Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 11 сентября 2012 г.
- Авторы: Misochko E.Y., Akimov A.V., Goldschleger I.U., Tyurin D.A., Laikov D.N.
- Журнал: Journal of Chemical Physics
- Том: 122
- Номер: 3
- Год издания: 2005
- Издательство: AIP Publishing
- Местоположение издательства: United States
- DOI: 10.1063/1.1829058
- Аннотация: Xenon fluoride radicals were generated by solid-state chemical reactions of mobile fluorine atoms with xenon atoms trapped in Ar matrix. Highly resolved electron spin resonance spectra of XeF. were obtained in the temperature range of 5-25 K and the anisotropic hyperfine parameters were determined for magnetic nuclei F-19, Xe-129, and Xe-131 using naturally occurring and isotopically enriched xenon. Signs of parallel and perpendicular hyperfine components were established from analysis of temperature changes in the spectra and from numerical solutions of the spin Hamiltonian for two nonequivalent magnetic nuclei. Thus, the complete set of components of hyperfine- and g-factor tensors of XeF. were obtained: F-19 (A(iso)=435, A(dip)=1249MHz) and Xe-129 (A(iso) = NO -1340, A(dip)= -485 MHz); g(\\) = 1.9822 and g(perpendicular to) = 2.0570. Comparison of the measured hyperfine parameters with those predicted by density-functional theory (DFT) calculations indicates, that relativistic DFT gives true electron spin distribution in the (2)Sigma(+) ground-state, whereas nonrelativistic theory underestimates dramatically the electron-nuclear contact Fermi interaction (A(iso)) on the Xe atom. Analysis of the obtained magnetic-dipole interaction constants (A(dip)) shows that fluorine 2p and xenon 5p atomic orbitals make a major contribution to the spin density distribution in XeF.. Both relativistic and nonrelativistic calculations give close magnetic-dipole interaction constants, which are in agreement with the measured values. The other relativistic feature is considerable anisotropy of g-tensor, which results from spin-orbit interaction. The orbital contribution appears due to mixing of the ionic (2)Pi states with the (2)Sigma(+) ground state, and the spin-orbit interaction plays a significant role in the chemical bonding of XeF.. (C) 2005 American Institute of Physics.
- Добавил в систему: Тюрин Даниил Александрович