Alternative Basis Sets for Accurate Quantum Chemistry

阿肯色大学的Peter Pulay得到了理论和计算化学计划的支持，以开发在电子结构计算中使用通常使用的高斯基组的替代方法。将探索平面波、小波、斯莱特函数和半数值轨道在化学应用中的潜在应用。将开发一种基于高斯的局部电子关联方法，目标是通过使用伪自然轨道、包含梯度和为选定的分子局域部分编程高级关联方法来减少弱相互作用轨道对的局部基尺寸。这些改进技术的应用包括金属蛋白模型的结构和振动光谱。此外，还将开发基于碳氢化合物相关计算的精确氢键势函数。预计该项目中开发的新方法将显著改进化学和生化系统的计算建模。这一项目的研究利用了计算机行业在过去五年中的快速技术发展。特别是快速内存和磁盘容量的急剧扩展，使之有可能为目前化学和生物化学中使用的计算方法提供可行的替代方案。该项目的成功成果可能会改变计算化学的完成方式，在药物化学和材料科学等领域产生重大的工业影响。

Peter Pulay of the University of Arkansas is supported by the Theoretical and Computational Chemistry Program to develop methods using alternatives to the generally employed Gaussian basis sets in electronic structure calculations. Plane waves, wavelets, Slater functions, and semi-numerical orbitals will be explored for their potential implementation in chemical applications. A Gaussian-based local electron correlation method will be developed, with goals of reduction of the local basis size for weakly interacting orbital pairs by using pseudo-natural orbitals, inclusion of gradients, and programming of high-level correlation methods for selected localized parts of a molecule. Application of these improved techniques include the structures and vibrational spectra of metalloprotein models. Also, accurate hydrogen bond potential functions based on correlated calculations for hydrocarbons will be developed. It is anticipated that the new methods developed in this project will significantly improve computational modeling of chemical and biochemical systems. The research in this project takes advantage of the rapid technological developments in the computer industry in the past five years. The dramatic expansion in fast memory and disk capacity, in particular, makes it possible to offer viable alternatives to the computational methods presently used in chemistry and biochemistry. Successful outcomes from this project could change the way computational chemistry is done, with substantial industrial impacts in areas such as pharmaceutical chemistry and materials science.