title: Electron spin echo envelope modulation of molecular motions of deuterium nuclei.
abstract: Electron Spin Echo Envelope Modulation (ESEEM) spectroscopy is a powerful technique for the study of hyperfine interactions between an unpaired electron and nearby nuclei in solids, and is employed in quantitative structural studies. Here, we describe the use of ESEEM to study the slow motion of deuterium nuclei using their nuclear quadrupole resonance (NQR) line shapes. Two ESEEM techniques were employed: the conventional three-pulse ESEEM experiment, π/2 - τ - π/2 - T- π/2 - τ - echo, and the four-pulse ESEEM, π/2 - τ - π/2 - T/2 - π - T/2 - π/2 - τ - echo, with the time variable T scanned in both cases. The nitroxide free radical 4-tert-butyliminomethyl-2,2,5,5-tetramethyl(d12)-3-imidazoline-1-oxyl with four deuterated methyl groups was investigated in a glassy ortho-terphenyl matrix over a wide temperature range. It was shown that four-pulse ESEEM allowed measurement of the nearly pure (2)H NQR line shape. Between 90K and 120K, the ESEEM spectra change drastically. At low temperatures, four-pulse ESEEM spectra show a Pake-like pattern, which evolves into a single line at higher temperatures, which is typical for NQR of rotating methyl CD3 groups. Comparison with literature data on NQR allows estimation of the reorientation rate, k. At ∼100K, where the spectral changes are most pronounced, k was found to be ∼10(5)s(-1). The spectral linewidths for the three-pulse ESEEM were found to decrease similarly with increasing temperature; so the three-pulse technique is also capable to detect motion of this type. The ESEEM approach, along with site-directed spin labeling, may be useful for detection of motional transitions near the spin labels in biological systems, when information on motion is required in a wide temperature range.
authors.affiliation: Voevodsky Institute of Chemical Kinetics and Combustion, Russian Academy of Sciences, 630090 Novosibirsk, Russia; Novosibirsk State University, 630090 Novosibirsk, Russia.
authors.forename: V N
authors.initials: VN
authors.lastname: Syryamina
authors.affiliation: Voevodsky Institute of Chemical Kinetics and Combustion, Russian Academy of Sciences, 630090 Novosibirsk, Russia.
authors.forename: A G
authors.initials: AG
authors.lastname: Maryasov
authors.affiliation: Department of Chemistry, The University of Alabama, Box 870336, Tuscaloosa, AL 35487-0336, USA.
authors.forename: M K
authors.initials: MK
authors.lastname: Bowman
authors.affiliation: Voevodsky Institute of Chemical Kinetics and Combustion, Russian Academy of Sciences, 630090 Novosibirsk, Russia; Novosibirsk State University, 630090 Novosibirsk, Russia. Electronic address: dzuba@kinetics.nsc.ru.
authors.forename: S A
authors.initials: SA
authors.lastname: Dzuba
mesh_terms: D000465:Algorithms; D003903:Deuterium / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods*; D005583:Fourier Analysis; D026361:Reactive Nitrogen Species / Q000737:chemistry; D013696:Temperature
chemical_list: D026361:Reactive Nitrogen Species; D003903:Deuterium
keywords: (2)H NQR; ESEEM; Molecular motions; Solvation shell; Spin label