Quantum Geochemistry

直接计算发生在矿物和水热溶液中的化学物质的结构和光谱特性将使用分子量子化学的成熟技术进行。对于第一过渡系金属的卤化物、氧化物和硫化物配合物，P.I.它将计算平衡结构、振动频率和电场梯度。他们将研究溶液中存在的配合物，如水化Zn(SH)n2-n，以及矿物中出现的物种的分子簇模型，如Fe(OH2)62+。这项研究的一个目标是鼓励在地球化学中使用过渡金属核磁共振。他们还将使用传统的SCF方法计算各种氧化物和硫化物环境中Fe的穆斯堡尔参数（化学异构体位移和电场梯度）。他们将继续研究含硫配体的电子性质及其与过渡金属的相互作用。他们还将继续我们对含有B、Al、Si和p的氧化分子的极化率和核磁共振屏蔽的研究。他们计划研究不对称物质的极化率各向异性，并更准确地包括反离子的影响。同样，对硅酸盐各向同性核磁共振屏蔽的研究将扩展到研究低对称环境下的核磁共振各向异性。最后，对小环系统进行一系列的实验和理论研究。

Direct calculation of the structural and spectral properties of chemical species occurring in minerals and in hydrothermal solutions will be performed using proven techniques from molecular quantum chemistry. For halide, oxide and sulfide complexes of 1st transition series metals the P.I.'s will calculate equilibrium structures, vibrational frequencies and electric field gradients. They will study both complexes existing in solution, such as aquated Zn(SH)n2-n, and molecular cluster models for species occurring in minerals, such as Fe(OH2)62+. One goal of the study will be to encourage the use of transition metal NMR within geochemistry. They will also calculate Mossbauer parameters (chemical isomer shift and electric field gradient) for Fe in various oxide and sulfide environments using conventional SCF methods. They will continue their studies of the electronic properties of sulfur containing ligands and their interaction with transition metals. They will also continue our studies of polarizabilities and NMR shieldings of oxidic molecules containing B, Al, Si and P. They plan to study polarizability anisotropies for less symmetric species and to more accurately include the influence of counterions. Similarly, studies of isotropic NMR shieldings for silicate species will be extended to study NMR anisotropies in lower symmetry environments. Finally, a series of experiments and theoretical studies will be completed for small ring systems.