EPR investigation of the methyl radical,the hydrogen atom and carbon oxide radicals in Maxixe-type beryl     

Lars Olov Andersson 《Physics and Chemistry of Minerals》2008,35(9):505-520

The EPR spectra of Maxixe-type beryl contain a large number of overlapping signals. The angular dependence of the 1:3:3:1 signal typical for the CH₃ radical shows that this radical is located at the center of the channel cavity with its symmetry axis parallel to the crystal c-axis and is rotating around this axis. Its EPR spectrum is axially symmetric with g _// = 2.00263, g _⊥ = 2.00249 and A_// = 2.288 mT, A_⊥ = 2.256 mT. These anisotropies have the opposite signs of those found for surface-adsorbed methyl radicals. Hydrogen atoms are located at position 2a at the center of the beryl cavity and the EPR parameters of the narrow doublet signal are A ₀ = 1,407 MHz and g = 2.00230. Another doublet signal, which is broader and has axial symmetry with g _// = 2.00265, g _⊥ = 2.00625 and A_// = 0.895 mT, A_⊥ = 0.885 mT, could come from a HCO₃ radical. One narrow and easily saturated signal with g _// = 2.00227 and g _⊥ = 2.00386 is interpreted to arise from a carbon monoxide radical in the beryl channel, oriented with its axis parallel to the crystal c-axis. Additional weak doublet lines, which have similar g values as the carbon monoxide radical, are created by nearby hydrogens. A powder spectrum with g _// = 2.0017 and g _⊥ = 2.0004 appears upon UV irradiation of the single crystal and is easily saturated. This spectrum is interpreted to arise from a carbon dioxide radical, which rotates around its symmetry axis.  相似文献   

Application of electron paramagnetic resonance spectroscopy to examination of carbonized coal blends     

B. Pilawa  S. Pusz  M. Krzesi&#x;ska  A. Koszorek  B. Kwieci&#x;ska 《International Journal of Coal Geology》2009,77(3-4):372-376

Paramagnetic centers in two- and three-component coal blends carbonized at 1000 °C were studied by X-band (9.3 GHz) electron paramagnetic resonance (EPR) technique. The blends were prepared from three different Polish coals with carbon contents [wt.%]: 88.66, 86.21, and 82.67, respectively. The aim of this work was to compare EPR parameters and concentrations of paramagnetic centers in the initial and carbonized coal samples. Furthermore the spin–spin and spin–lattice interactions were characterized.EPR spectra were measured with magnetic modulation 100 kHz and microwave power 0.7 mW. Amplitudes and linewidths of EPR spectra were obtained. g-Factors were calculated from resonance condition. Concentrations of paramagnetic centers in the samples were determined. Influence of microwave power in the range 0.7–70 mW on EPR spectra was analyzed.All the studied samples revealed paramagnetism. Unpaired electrons are localized in the same atoms, because similar g-values in the range 2.0035–2.0038 were obtained for all the original samples. The EPR parameters of coal blends were additive in comparison with the parent coals. EPR spectra strongly changed after carbonization of the coal samples. Narrower EPR lines were measured for the original coal samples than for carbonized ones. We detected lower concentrations of paramagnetic centers in carbonized three-component coal blends than in two-component carbonized blends. EPR lines of the studied carbonized blends were not saturated at the microwave power used, which suggests fast spin–lattice relaxation processes in the samples. EPR examination proved chemical interactions between coal constituents during carbonization of coal blends.  相似文献   

Radiation-induced defects in quartz. III. Single-crystal EPR,ENDOR and ESEEM study of a peroxy radical     

Mark J. Nilges  Yuanming Pan  Rudolf I. Mashkovtsev 《Physics and Chemistry of Minerals》2009,36(2):61-73

The X- and W-band single-crystal electron paramagnetic resonance spectra of an electron-irradiated natural quartz permit quantitative analysis of a ²⁹Si hyperfine structure (A ~12.6 MHz) and an ²⁷Al hyperfine structure (A ≤ 0.8 MHz) for a previously reported hole-like center. The ²⁹Si hyperfine structure arises from interaction with two equivalent Si atoms and is characterized by the direction of the unique A axis close to a Si–O bond direction. The ²⁷Al hyperfine structure, confirmed by pulsed electron nuclear double resonance and electron spin echo envelope modulation spectra, is characterized by the unique A axis approximately along a twofold symmetry axis. These ²⁹Si and ²⁷Al hyperfine data, together with published theoretical results on peroxy radicals in SiO₂ as well as our own density functional theory (DFT) calculations on model peroxy centers, suggest this hole-like center to have the unpaired spin on a pair of oxygen atoms linked to two symmetrically equivalent Si atoms and a substitutional Al³⁺ ion across the c-axis channel, a first peroxy radical in quartz. The nuclear quadrupole matrix P also suggests that the Al³⁺ ion corresponds closely to the diamagnetic precursor to the [AlO₄]⁰ center. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

Induced modifications of kaolinite under ionizing radiation: an infrared spectroscopic study     

C. Fourdrin  E. Balan  T. Allard  C. Boukari  G. Calas 《Physics and Chemistry of Minerals》2009,36(5):291-299

Radiation effects on kaolinite were investigated using He⁺ ions of 1.5 MeV at radiation doses up to 4.3 × 10⁸ Gy, which are comparable to the doses expected for clay barriers in high-level nuclear waste repositories. The concentration of paramagnetic radiation-induced defects in kaolinite reaches 2 × 10¹⁶ spins/mg (400 at. ppm), as determined by electron paramagnetic resonance spectroscopy. The broadening of X-ray diffraction patterns and transmission infrared (IR) absorption bands is mostly related to the structural strain induced by radiation-induced point defects. The broadening of IR absorption spectra is analyzed using an autocorrelation approach and is related to a change in the distribution of vibrational frequencies due to crystal heterogeneities. We theoretically analyze how the effective dielectric properties of kaolinite samples depend on macroscopic parameters and how irradiation can modify some of them. Irradiation leads to an increase in the electronic polarizability of kaolinite particles, related to the accumulation of radiation-induced electronic point defects.  相似文献   

Native and artificial radiation-induced defects in montmorillonite. An EPR study     

S. Sorieul  T. Allard  G. Morin  B. Boizot  G. Calas 《Physics and Chemistry of Minerals》2005,32(1):1-7

A natural montmorillonite containing radiation-induced defects was studied with Electron Paramagnetic Resonance (EPR) spectroscopy (X- and Q-band). A first dominant native defect, namely native defect 1, is identified. It gives rise to an orthorhombic spectrum with g_x= 2.004 ± 0.005 g_y= 2.010 ± 0.003, g_z= 2.065 ± 0.002. Simulation of the EPR spectrum at X- and Q-band reveals a second native defect with isotropic spectrum at g= 2.019 ± 0.005. Both are electron holes trapped on oxygen atoms of the structure. The native defect 1 is located on an oxygen-silicon bond or a non-bonding orbital parallel to the c* axis. These defects are annealed at 500°C and the half-life determined for native defect 1 is circa 3,000 years. Irradiations with beta rays produced two additional hole centers of lower stability and distinct EPR parameters. Artificial irradiations show that montmorillonite can be used as a dosimeter in a large dose range.  相似文献   

Formation of hydroxyl radicals catalyzed by clay surfaces     

D. Gournis  M. A. Karakassides  D. Petridis 《Physics and Chemistry of Minerals》2002,29(2):155-158

 The formation of superoxide and hydroxyl radicals at the surface of smectite clays due to oxygen reduction is demonstrated by electron paramagnetic resonance spectroscopy. The yield of hydroxyl radicals is mainly a function of particle size of the clays and depends, to a lesser extent, on the clay lattice iron. Synthetic laponite clay with small platelet size (∼20 nm) and without lattice iron is leading in the formation of hydroxyl radicals followed by montmorillonite (∼200 nm). Fluorohectorite (∼2000 nm) was inactive to hydroxyl radical formation by oxygen reduction. Received: 20 January 2001 / Accepted: 7 August 2001  相似文献   

Incorporation of Cr<Superscript>3+</Superscript> in dickite: a spectroscopic study     

E. Balan  T. Allard  G. Morin  G. Calas 《Physics and Chemistry of Minerals》2002,29(4):273-279

 We have investigated a well-ordered sample of natural Cr-bearing dickite from Nowa Ruda (Lower Silesia, Poland) using electron paramagnetic resonance (EPR) at X- and Q-band frequencies (9.42 and 33.97 GHz, respectively) and optical diffuse reflectance spectroscopy. The observation of the spin-forbidden transitions at 15500 and 14690 cm⁻¹ allows us to unambiguously identify the major contribution of octahedrally coordinated Cr³⁺ ions in the optical spectrum. The X- and Q-band EPR spectra show two superposed Cr³⁺ signals. The corresponding fine-structure parameters were determined at room temperature and 145 K. These results suggest the substitution of Cr³⁺ for Al³⁺ in equal proportions in the two unequivalent octahedral sites of the dickite structure. In kaolin group minerals, the distortion around Cr³⁺ ions (λ≈ 0.2–0.4) in Al sites is significantly less rhombic than that observed around Fe³⁺ ions (λ≈ 0.6–0.8). Received: 29 June 2001 / Accepted: 22 October 2001  相似文献   

天然叶蜡石及其热处理产物的电子顺磁共振（EPR）研究   总被引：7，自引：2，他引：7  

蔡秀成  张惠芬等 《矿物学报》1990,10(1):15-22

利用EPR研究了18个天然叶蜡石样及其4个热处理产物。发现天然叶蜡石有三个EPR吸收带：A（g有效≈11．4），B（g有效≈4．3）和C（g有效≈2．0），其中A是叶蜡石的特征谱。A在＞400℃热处理时与B在强度上呈消长关系；＜400℃热处理时A和B均随温度升高而加强；900℃时A消失，B的强度远远大于原样中的A；C附有超精细结构谱（g″=2.04,g┴=1.96,A″≈A┴=19.5×10^-4T），C在热处理时呈现复杂的变化。结果表明，A吸收带属于叶蜡石八面体AI（Fe)-O4(OH)2中的Fe^3 ，B吸收带归于八面体AI（Fe)-O2(OH)4中的Fe^3 ，C吸收带是无机自由基（如AI－O^-Si)和有机自由基的叠加谱；900℃热处理后八面体层中配位发生了变化：AI（Fe)-O4(OH2)→AI（Fe)-O5 H2O↑，AI(Fe)-O2(OH)4→AI(Fe)-O4 H2O↑；类质同象置换AI^3 的不仅有Fe^3 ,而且有Fe^2 离子。  相似文献   

波伏棱（Povlen）型羟基纤蛇纹石的谱学研究     

朱和宝  江绍英  邵涵如  吴卫芳 《岩石矿物学杂志》1989,8(1):43-53

波伏棱型羟基纤蛇纹石是波伏棱型纤蛇纹石矿物的新变种,本文报导它的吸收光谱、红外光谱、穆斯堡尔谱、电子顺磁共振谱和核磁共振谱。 研究表明,吸收光谱是Fe~(3 )和Fe~(2 )的晶场跃迁以及Fe~(2 )→Fe~(3 )的荷移跃迁引起的;红外光谱是OH和Si-O的伸缩振动、OH转动以及Mg-O和Si-O的弯曲振动引起的;穆斯堡尔谱是Fe~(2 )_(八面体)、Fe~(3 )_(八面体)和Fe~(3 )_(四面体)引起的;电子顺磁共振谱是Mn~(2 )_(八面体)、Fe~(3 )_(八面体)和Fe~(3 )_(四面体)引起的;核磁共振谱是管道水,镁八面体和硅氧四面体上的OH引起的;矿物加热到825℃时,结构开始破坏并出现镁橄榄石相。 此外,本文还解释了该蛇纹石颜色的本质,阐明了上述过渡金属离子和OH在该矿物中的结构环境。  相似文献   

方解石中Mn~(2+)离子四级EPR晶场参量α_0随温度变化的研究     

郑文琛 《矿物学报》1988,(4)

本文研究表明,对方解石中Mn~(2+)离子的四级EPR晶场参量α_0,虽然其轴向场部分的贡献远小于立方场部分,但二者随温度的变化却差别不大,原因是轴向晶场参量F对键角变化十分敏感。因此,在研究热膨胀系数明显各向异性的晶体中的α_0随温度变化时,不能忽略轴向场部分的贡献,即不能假设α_0≈-α。  相似文献