Systematic Gaussian basis‐set limit using completeness‐optimized primitive sets. A case for magnetic properties
Systematic Gaussian basis‐set limit using completeness‐optimized primitive sets. A case for magnetic properties
复制标题
使用完整性优化基元集的系统高斯基组限制磁特性的案例。
DOI：
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发表时间：
2006
影响因子：
3
通讯作者：
J. Vaara
中科院分区：
文献类型：
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作者：
P. Manninen;J. Vaara
我们讨论了由Chong(Can J Chem 1995，73，79)提出的在某个指数区间的完备性轮廓来衡量基集的完备性，以及在靠近原子核的区域或在价区重现分子性质的可能性之间的联系。我们提出了一种生成完备性优化高斯基集合的方案，在该方案中，预先选择的指数范围被覆盖到任意精度。这是通过要求高斯函数(其指数是在不参考原子结构的情况下选择的)以尽可能少的函数以尽可能接近于所需的整体性分布的范围跨越的来实现的。初始指数范围可以选择适合于分子能量学或其他类价性质的计算。通过扩展指数范围，可以直接和系统地处理在给定角动量值和/或在给定距离范围内需要增大基数的性质。在该方案中，以自动的方式生成通用的、与元素无关的指数集。用完备性优化的基集和文献中的基集检验了基集完备性与计算磁化率、核磁屏蔽和自旋-自旋耦合的性能之间的关系。©2006威利期刊，Inc.康普特化学杂志27：434-445,2006
We discuss the connection between the completeness of a basis set, measured by the completeness profiles introduced by Chong (Can J Chem 1995, 73, 79) at a certain exponent interval, and the possibility of reproducing molecular properties that arise either in the region close to the atomic nuclei or in the valence region. We present a scheme for generating completeness‐optimized Gaussian basis sets, in which a preselected range of exponents is covered to an arbitrary accuracy. This is done by requiring Gaussian functions, the exponents of which are selected without reference to the atomic structure, to span the range with completeness profile as close to unity as wanted with as few functions as possible. The initial exponent range can be chosen suitable for calculations of molecular energetics or other valence‐like properties. By extending the exponent range, properties requiring augmentation of the basis at a given angular momentum value and/or in a given distance range from the nucleus may be straightforwardly and systematically treated. In this scheme a universal, element‐independent exponent set is generated in an automated way. The relation of basis‐set completeness and performance in the calculation of magnetizability, nuclear magnetic shielding, and spin–spin coupling is tested with the completeness‐optimized primitive sets and literature basis sets. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 434–445, 2006