Correlations between 29Si, 17O and 1H NMR properties and local structures in silicates: an ab initio calculation

In order to gain insight into the correlations between ²⁹Si, ¹⁷O and ¹H NMR properties (chemical shift and quadrupolar coupling parameters) and local structures in silicates, ab initio self-consistent field Hartree-Fock molecular orbital calculations have been carried out on silicate clusters of various polymerizations and intertetrahedral (Si-O-Si) angles. These include Si(OH)₄ monomers (isolated as well as interacting), Si₂O(OH)₆ dimers (C₂ symmetry) with the Si-O-Si angle fixed at 5° intervals from 120° to 180°, Si₃O₂(OH)₈ linear trimers (C₂ symmetry) with varying Si-O-Si angles, Si₃O₃(OH)₆ three-membered rings (D₃ and C₁ symmetries), Si₄O₄(OH)₈ four-membered ring (C₄ symmetry) and Si₈O₁₂(OH)₈ octamer (D₄ symmetry). The calculated ²⁹Si, ¹⁷O and ¹H isotropic chemical shifts (δ_i ^Si, δ_i ^O and δ_i ^H) for these clusters are all close to experimental NMR data for similar local structures in crystalline silicates. The calculated ¹⁷O quadrupolar coupling constants (QCC) of the bridging oxygens (Si-O-Si) are also in good agreement with experimental data. The calculated ¹⁷O QCC of silanols (Si-O-H) are much larger than those of the bridging oxygens, but unfortunately there are no experimental data for similar groups in well-characterized crystalline phases for comparison. There is a good correlation between δ_i ^Si and the mean Si-O-Si angle for both Q ¹ and Q ², where Q ⁿ denotes Si with n other tetrahedral Si next-nearest neighbors. Both the δ _i ^O and the ¹⁷O electric field gradient asymmetry parameter, η of the bridging oxygens have been found to depend strongly on the O site symmetry, in addition to the Si-O-Si angle. On the other hand, the ¹⁷O QCC seems to be influenced little by structural parameters other than the Si-O-Si angle, and is thus expected to be the most reliable ¹⁷O NMR parameter that can be used to decipher Si-O-Si angle distribution information. Both the ¹⁷O QCC and the ²H QCC of silanols decrease with decreasing length of hydrogen bond to a second O atom (Si-O-H···O), and the δ _i ^H increase with the same parameter. Received: 18 July 1997 / Revised, accepted: 23 February 1998     

Dissolution mechanisms of water in depolymerized silicate melts: Constraints from H and Si NMR spectroscopy and ab initio calculations

Dissolution of water in magmas significantly affects phase relations and physical properties. To shed new light on the this issue, we have applied ¹H and ²⁹Si nuclear magnetic resonance (NMR) spectroscopic techniques to hydrous silicate glasses (quenched melts) in the CaO-MgO-SiO₂ (CMS), Na₂O-SiO₂, Na₂O-CaO-SiO₂ and Li₂O-SiO₂ systems. We have also carried out ab initio molecular orbital calculations on representative clusters to gain insight into the experimental results.The most prominent result is the identification of a major peak at ∼1.1 to 1.7 ppm in the ¹H MAS NMR spectra for all the hydrous CMS glasses. On the basis of experimental NMR data for crystalline phases and ab initio calculation results, this peak can be unambiguously attributed to (Ca,Mg)OH groups. Such OH groups, like free oxygens, are only linked to metal cations, but not part of the silicate network, and are thus referred to as free hydroxyls in the paper. This represents the first direct evidence for a substantial proportion (∼13∼29%) of the dissolved water as free hydroxyl groups in quenched hydrous silicate melts. We have found that free hydroxyls are favored by (1) more depolymerized melts and (2) network-modifying cations of higher field strength (Z/R²: Z: charge, R: cation-oxygen bond length) in the order Mg > Ca > Na. Their formation is expected to cause an increase in the melt polymerization, contrary to the effect of SiOH formation. The ²⁹Si MAS NMR results are consistent with such an interpretation. This water dissolution mechanism could be particularly important for ultramafic and mafic magmas.The ¹H MAS NMR spectra for glasses of all the studied compositions contain peaks in the 4 to 17 ppm region, attributable to SiOH of a range of strength of hydrogen bonding and molecular H₂O. The relative population of SiOH with strong hydrogen bonding grows with decreasing field strength of the network-modifying cations. Ab initio calculations confirmed that this trend largely reflects hydrogen bonding with nonbridging oxygens.     

富氯造岩矿物中溴的分子结构

卤族元素诸如氯和溴作为地球化学示踪剂,常用于指示岩浆、变质岩和热液的来源和演化过程。而认清溴在造岩矿物中的形态和结构有助于丰富和完善其在地质环境演变中的示踪作用。但是,溴在造岩矿物中的含量极低导致大多数结构分析方法都无法使用,因此造岩矿物中微量溴的结构研究极具挑战性。本文采用 ⁸¹Br魔角旋转核磁共振(MAS NMR)光谱和同步辐射吸收光谱(XAS)技术,首次对富氯造岩矿物中的微量溴进行了结构分析。结果表明溴离子在方硼石中的微区结构不同于该矿物中三配位Cl原子的结构环境,而与Mg₃B₇O₁₃Br中八面体配位的溴离子相似,表明即使在微量条件下也存在域偏析。而对其他富氯造岩矿物的Br K边X光吸收近边结构(XANES)光谱白线峰的位置和扩展X射线吸收精细结构(EXAFS)分析表明微量溴离子替代了这些矿物中氯的位置,导致局部结构扭曲膨胀。溴离子在造岩矿物中的这一微观结构研究结果可为探索氯和溴在地质演变过程的指示作用提供新的科学依据。     

Water solubility in nominally anhydrous minerals measured by FTIR and 1H MAS NMR: the effect of sample preparation

Samples of enstatite and forsterite were crystallized in the presence of a hydrous fluid at 15 kbar and 1100 °C. Water contents in quenched samples were measured by ¹H MAS NMR and by FTIR. If the samples were prepared in the same way, similar water concentrations were obtained by both methods. There is no evidence that one or the other method would severely over or underestimate water contents in nominally anhydrous minerals. However, measured water contents vary by orders of magnitude depending on sample preparation. The lowest water contents are measured by polarized FTIR spectroscopy on clear, inclusion-free single crystals. These water contents probably reflect the real point defect solubility in the crystals. Polycrystalline material shows much higher total water concentrations, presumably due to hydrous species on grain boundaries, growth defects, and in submicroscopic fluid inclusions. Grinding the sample in air further increases water concentration. This effect is even more pronounced if the sample is ground in water and subsequently dried at 150 °C. Polarized FTIR measurements on clear single crystals of enstatite saturated at 15 kbar and 1100 °C give 199 ± 25 ppm by weight of water. The spectra show sharp and strongly polarized bands. These bands are also present in spectra measured through turbid, polycrystalline aggregates of enstatite. However, in these spectra, they are superimposed on much broader, nearly isotropic bands resulting from hydrous species in grain boundaries, growth defects, and submicroscopic fluid or melt inclusions. Total water contents for these polycrystalline aggregates are between 2000 and 4000 ppm. Water contents measured by FTIR on enstatite powders are 5300 ppm after grinding in air and 12 600 ppm after grinding under water und subsequent drying at 150 °C. Received: 25 June 1999 / Revised, accepted: 4 October 1999     

Ab initio calculations of 17O and nT NMR parameters (nT=31P, 29Si) in H3 TOTH3 dimers and T 3O9 trimeric rings

NMR shieldings (σ) and electric field gradients (eq) are calculated using ab initio methods at the O and T nuclei (where T=P, Si) in two different types of molecules-TH₃ dimers, i.e. H₃SiOSiH₃ and H₃POPH ₃ ²⁺ , and TO₄ trimeric rings, i.e., Si₃O ₉ ^6- and P₃O ₉ ^3- , which serve as models for assessing the effects of polymerization, bond length and bond angle variation on the NMR properties of polymerized silicates and phosphates. In agreement with earlier ab initio studies on H₃SiOSiH₃ we confirm that σ(²⁹Si), σ(³¹P), σ(¹⁷O) and eq(¹⁷O) all decrease as θ(SiOSi) decreases in the range from 180° to 100°. However, correction for artifacts due to distant core electrons leads to a considerably reduced value for the anisotropy in σ ^O, bringing it into better agreement with estimated experimental values. The qualitative change in σ(²⁹Si) with θ(SiOSi) can be understood on the basis of changes in the energies of the highest energy occupied MO's and consequent variations in their contributions to the paramagnetic part of the shielding. For H₃POPH ₃ ²⁺ we calculate a larger value of eq^O than for the analog Si compound but the same type of variation of σ(¹⁷O) with θ(TOT). The change in σ(³¹P) with θ(POP) is, however, calculated to be much smaller than in the Si case and a maximum is predicted for intermediate angles. For the trimeric rings we obtain energy optimized geometries in good agreement with x-ray structural data, with T-O terminal distances systematically shorter than the T-O bridging distances. Calculated σ(T) anisotropies are also in good agreement with experiment and can be simply related to the calculated structure. After correction for distant core effects we obtain a change in σ(³¹P) between PO ₄ ^3- and P₃O ₉ ^3- in reasonable agreement with experiment.