...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Metal—Ligand Bonds of Second- and Third-Row d-Block Metals Characterized by DensityFunctional Theory
【24h】

Metal—Ligand Bonds of Second- and Third-Row d-Block Metals Characterized by DensityFunctional Theory

机译：用密度泛函理论表征第二行和第三行d族金属的金属配体键

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

This paper presents systematic data for 200 neutral diatomic molecules ML (M is a second- or third-rowd-block metal and L = H, F, Cl, Br, I, C, N, 0, S, or Se) computed with the density functionals TPSSh andBP86. With experimental structures and bond enthalpies available for many of these molecules, the computationsfirst document the high accuracy of TPSSh, giving metal—ligand bond lengths with a mean absolute error of～0.01 ? for the second row and 0.03 third row. TPSSh provides metal—ligand bond enthalpieswith mean absolute errors of 37 and 44 kJ/mol for the second- and third-row molecules, respectively.Pathological cases (e.g., HgC and H_gN) have errors of up to 155 kJ/mol, more than thrice the mean (observedwith both functionals). Importantly,thesystematic error Component is negligible as measured by a coefficientof the linear regression line of 0.99 Equally important, TPSSh provides uniform accuracy across all threerows of the d-block, which is unprecedented and due to the 10% exact exchange, which is close to optimalfor the d-block as a whole. This work provides an accurate and systematic prediction of electronic ground-state spins, characteristic metal—ligand bond lengths, and bond enthalpies for many as yet uncharacterizeddiatomics, of interest to researchers in the field of second- and third-row d-block chemistry. We stress thatthe success of TPSSh cannot be naively extrapolated to other special situations such as, e.g., metal—metalbonds. The high accuracy of the procedure further implies that the effective core functions used to modelrelativistic effects are necessary and sufficient for obtaining accurate geometries and bond enthalpies of second-and third-row molecular systems.
机译：本文介绍了用以下公式计算的200个中性双原子分子ML（M是第二或第三排金属，L = H，F，Cl，Br，I，C，N，0，S或Se）的系统数据密度泛函TPSSh和BP86。利用这些分子中许多分子的实验结构和键焓，计算首先证明了TPSSh的高精度，给出了金属-配体键长，平均绝对误差为〜0.01？。第二行和0.03第三行。 TPSSh可提供第二行和第三行分子的金属-配体键焓，平均绝对误差分别为37和44 kJ / mol。病理情况（例如，HgC和H_gN）的误差高达155 kJ / mol，大于平均值的三倍（同时观察两个功能）。重要的是，通过线性回归线的系数0.99测得的系统误差分量可以忽略。对于整个d块而言是最佳的。这项工作为第二和第三行d嵌段化学领域的研究人员所感兴趣的，为许多尚未表征的硅原子提供了电子基态自旋，特征性金属-配体键长以及键焓的准确而系统的预测。我们强调，TPSSh的成功不能天真地推论到其他特殊情况，例如金属-金属键。该方法的高精度还意味着，用于对相对论效应进行建模的有效核心功能对于获得第二行和第三行分子系统的精确几何形状和键焓是必要且充分的。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号