随机相近似方法的一般性扰动单项校正:对封闭和开放二分体的非共价相互作用能量的影响
Pulkit Joshi1, Vamsee K Voora1
1Department of Chemical Sciences, Tata Institute of Fundamental Research, Homi Bhabha Road, Colaba, Mumbai 400005, India.
The Journal of chemical physics
|January 23, 2024
概括
我们开发了一种新的方法来改进对弱键分子的相互作用能量计算. 这种RPA单项 (RPAS) 校正显著提高了开系统的准确性,在非共价相互作用中实现了化学准确性.
科学领域:
- 计算化学是一种计算化学.
- 量子化学是一种量子化学.
- 理论化学是一种理论化学.
背景情况:
- 后科恩-沙姆 (KS) 随机相近似 (RPA) 由于近似KS函数的密度错误,与弱结合分子的相互作用能量作斗争.
- 准确计算非共价相互作用对于理解分子行为和化学反应至关重要.
研究的目的:
- 为RPA方法的扰动单项 (pS) 校正开发一个通用的形式主义.
- 改进对弱键分子,特别是开系统的相互作用能量的描述.
主要方法:
- 开发了一种通用形式主义,使用轨道旋转作为扰动参数进行扰动单元 (pS) 校正.
- 提出了一个特定的ps方案,RPA单元 (RPAS) [哈特里-福克 (HF) ],利用RPA轨道旋转梯度和时间依赖的哈特里-福克 (HF) 赫西安.
- 将RPAS (HF) 校正应用于封闭和开放的二次体,以评估非共价相互作用能量.
主要成果:
- RPAS (HF) 校正显著降低了非对应相互作用能量的错误,无论是封闭的还是开放的二次体.
- 对于开二元体,RPAS (HF) 与标准RPA方法相比,在各种相互作用类型 (结合,金属溶剂,碳溶剂,分散) 中,始终可以将误差降低50%或更多.
- 发现扰乱性单个校正对于减少错误比RPA方法的更高阶交换校正更为关键.
结论:
- 经RPAS (HF) 校正的RPA方法在开系统中实现非共价相互作用的化学精度.
- 这种超RPA校正比其他扰动方案和分散校正密度函数近似更可靠,使其成为准确计算化学的宝贵工具.
- 开发的形式主义提供了一个强大的方法来提高基于RPA的方法的准确性,用于研究分子相互作用.
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