数字稳定的共振哈特里-福克
Ericka Roy Miller1, Shane M Parker1
1Department of Chemistry, Case Western Reserve University, 10900 Euclid Ave, Cleveland, Ohio 44106, USA.
我们介绍了一种稳定的共振哈特里-福克 (ResHF) 方法来模拟激发状态,改善波函数优化. 这种计算效率高的方法对电子结构计算具有前景.
科学领域:
- 计算化学计算化学
- 量子化学 是一个量子化学.
- 电子结构理论 电子结构理论
背景情况:
- 高效模拟兴奋状态是电子结构 (ES) 方法的一个重大挑战.
- 现有的正交ES方法有局限性,对于激发状态的非正交方法,特别是与非正交轨道优化,研究较少.
- 在处理近直角轨道的方法中,常常会出现数值不稳定.
研究的目的:
- 为激发状态计算开发共振哈特里-福克 (ResHF) 方法的数值稳定的配方.
- 在ResHF方法中改进波函数优化过程.
- 将改进的ResHF方法的性能与完整的活性空间自相一致场 (CASSCF) 等既有方法进行比较.
主要方法:
- 介绍了共振哈特里-福克 (ResHF) 方法的数值稳定的配方.
- 利用矩阵附加物来减轻由近直角轨道引起的数值不稳定性.
- 在各种化学系统中对CASSCF进行基准ResHF比较,包括LiF避免了交叉,乙烯扭转和小分子中的单元-三元能量差距.
主要成果:
- 由于新配方,在ResHF波函数优化方面取得了显著的改进.
- ResHF准确地描述了兴奋状态,结合了轨道放松,同时保持了正确的状态交叉.
- 开源实现,yucca,可用于更广泛的使用.
结论:
- 稳定ResHF方法为激发状态模拟提供了一个有希望的,计算效率高的方法.
- 它结合了特定状态 (轨道放松) 和状态平均 (正确状态交叉) 方法的好处.
- 开发的ResHF实现为电子结构计算提供了有价值的工具.
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