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Shortly after de Broglie published his ideas that the electron in a hydrogen atom could be better thought of as being a circular standing wave instead of a particle moving in quantized circular orbits, Erwin Schrödinger extended de Broglie’s work by deriving what is now known as the Schrödinger equation. When Schrödinger applied his equation to hydrogen-like atoms, he was able to reproduce Bohr’s expression for the energy and, thus, the Rydberg formula governing hydrogen spectra.
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通过将电子哈密尔顿式与有效的短距离相互作用相结合来纠正波函数相关性能量的基础集不完整性.

Michał Hapka1, Aleksandra Tucholska2, Marcin Modrzejewski1

  • 1Faculty of Chemistry, University of Warsaw, ul. L. Pasteura 1, 02-093 Warsaw, Poland.

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概括
此摘要是机器生成的。

我们介绍了一种新方法,以减少电子相关性能量计算中的基数组错误. 这种方法提高了计算化学的准确性,在较小的基础集中实现了高精度.

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科学领域:

  • 计算化学的计算化学
  • 量子化学 是一个量子化学.
  • 理论化学 理论化学

背景情况:

  • 基准集的不完整性是电子结构计算中的一个重要错误来源.
  • 精确计算电子相关能量对于预测分子性质至关重要.

研究的目的:

  • 开发一种通用和有效的方法来减少电子相关性能量计算中的基数组不完整性误差.
  • 引入一种新的方法,在单个计算中计算校正.

主要方法:

  • 用有效的短距离相互作用修改电子相互作用运算符.
  • 库伦运算子的局部映射到使用范围分离参数的远程交互.
  • 应用程序具有完整的活跃空间波函数和线性增离子连接 (AC0) 或n电子价值状态二阶扰动理论 (NEVPT2).

主要成果:

  • 提出的方法有效地减少了基准设置不完整性错误.
  • 在三倍ζ基数组中计算的准确性与五倍ζ基数组中未经校正的方法相当或超过.
  • 对测试分子的相对能量获得了令人鼓舞的结果.

结论:

  • 开发的方法提供了一个计算效率高的方法来提高电子相关性能量计算的准确性.
  • 这种方法提供了一个可行的替代传统的基础设置推断或增强技术.
  • 这些发现表明,在降低计算成本的情况下实现高精度电子结构计算的重大进步.