可扩展的量子蒙特卡洛与直接产品试验波函数
Hung Q Pham1, Runsheng Ouyang2, Dingshun Lv3
1ByteDance Research, San Jose, California 95110, United States.
Journal of chemical theory and computation
|May 3, 2024
概括
我们为无相辅助场量子蒙特卡洛 (AFQMC) 引入了直接产品的多斯莱特决定试验,以降低强相关分子的计算成本. 当活动空间可分解时,这种方法提供了显著的加快速度,在非合或弱合子空间中保持准确性.
科学领域:
- 计算化学计算化学
- 量子蒙特卡洛方法 量子蒙特卡洛方法
- 电子结构理论 电子结构理论
背景情况:
- 无相辅助场量子蒙特卡罗 (AFQMC) 方法面临着高的计算需求,特别是对于具有强大的电子相关性分子.
- 目前的多斯莱特决定子 (MSD) 试验可能是计算密集的,限制了它们对复杂分子系统的应用.
研究的目的:
- 建议和评估使用直接产品波函数作为MSD-AFQMC的试验.
- 通过利用直接产品多斯莱特决定子 (DP-MSD) 试验的紧性来降低与MSD-AFQMC相关的计算开销.
- 评估DP-MSD试验对具有不同电子结构复杂性的分子系统的准确性和效率.
主要方法:
- 开发了一种使用直接产物波函数作为MSD-AFQMC试验的新方法.
- 定义"可分解的活性空间"是指可以将活性空间划分为非合子空间的条件.
- 采用局部活性空间自相一致场 (LASCF) 波函数作为DP-MSD试验,并对各种分子系统进行了测试.
主要成果:
- 在DP-MSD试验中,当活性空间可分解时,DP-MSD试验显著降低了计算成本,高达C2H6N4的36倍.
- 对于像二聚体这样的弱合系统,DP-MSD试验降低了计算成本,同时保持了与完整的活跃空间试验相比的准确性.
- 与完全活跃空间方法相比,具有强大的子空间合的系统的准确性下降.
结论:
- 直接产品的Slater多决定性试验在特定分子系统中为MSD-AFQMC提供了一个计算效率高的替代方案.
- 该方法对于不合到需要局部多引用处理的弱合子空间的系统特别有利.
- 需要仔细考虑子空间合,以确保准确性.
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