On the suitability of strictly localized orbitals for hybrid QM/MM calculations

In the QM/MM method we have developed (LSCF/MM), the QM and the MM parts are held together by means of strictly localized bonding orbitals (SLBOs). Generally these SLBOs are derived from localized bond orbitals (LBOs) that undergo tails deletion, resulting in a nonpredictable change of their properties. An alternative set of SLBOs is provided by the extremely localized molecular orbitals (ELMOs) approach, where the orbitals are rigorously localized on some prefixed atoms without tails on the other atoms of the molecule. A comparative study of SLBOs arising from various localization schemes and ELMOs is presented to test the reliability and the transferability of these functions within the Local Self-Consistent Field (LSCF) framework. Two types of chemical bonds were considered: C--C and C--O single bonds. The localized functions are obtained on the ethane and the methanol molecules, and are tested on beta-alanine and diethyl ether molecules. Moreover, the various protonation forms of beta-alanine have been investigated to illustrate how well the polarity variation of the chemical bond can be handled throughout a chemical process. At last, rotation energy profiles around C--C and C--O bonds are reproduced for butane and fluoromethanol. Energetic, geometric, as well as electronic factors all indicate that ELMO functions are much more transferable from one molecule to another, leading to results closer to the usual SCF reference than any other calculations involving any other localized orbitals. When the shape of the orbital is the most important factor then ELMO functions will perform as well as any other localized orbital.     

Radial‐template approach for accurate density representation in computational quantum theory

A method for improved representation of electronic charge and spin densities for molecular and solid state systems is presented, based upon extensions of least squares fits to quantum mechanical “true” densities using basis functions of limited support. Attention is given to optimization of radial degrees of fit freedom, and the design of fit functions permitting rapid analytic manipulation and calculation of properties, such as Coulomb potentials. The method is demonstrated for covalent CO and for a large metal‐organic crystalline structure. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

正交各向异性韧性材料应力-应变关系

采用大变形弹塑性有限元方法分析了各向同性和正交各向异性韧性材料光滑圆棒拉伸试件的颈缩问题．首先给出了采用计算机模拟确定各向同性韧性材料真实应力-应变曲线的具体方法；对正交各向异性韧性材料的分析表明，颈缩截面呈椭圆形，其长短轴方向的等效塑性应变基本上均匀分布，与Bridgman假设一致；轴向拉伸载荷-位移曲线与其它两方向的各向异性参数关系不大．在此基础上，建议了一种确定正交各向异性韧性材料真实应力-应变曲线的方法．