Response Formalism within Full Configuration Interaction Quantum Monte Carlo: Static Properties and Electrical Response,Journal of Chemical Theory and Computation

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Response Formalism within Full Configuration Interaction Quantum Monte Carlo: Static Properties and Electrical Response
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2018-06-13 00:00:00 , DOI: 10.1021/acs.jctc.8b00454
Pradipta Kumar Samanta _{1,

2} , Nick S. Blunt ₃ , George H. Booth ₄

Affiliation

We formulate a general, arbitrary-order stochastic response formalism within the full configuration interaction quantum Monte Carlo framework. This modified stochastic dynamic allows for the exact response properties of correlated multireference electronic systems to be systematically converged upon for systems far out of reach of traditional exact treatments. This requires a simultaneous coupled evolution of a response state alongside the zero-order state, which is shown to be stable, nontransient, and unbiased. We demonstrate this with application to the static dipole polarizability of molecular systems and, in doing so, resolve a discrepancy between restricted and unrestricted high-level coupled-cluster linear response results which were the high-accuracy benchmark in the literature.

中文翻译：

完全配置相互作用量子蒙特卡洛中的响应形式主义：静态特性和电响应

我们在完整的配置相互作用量子蒙特卡洛框架内制定了一种一般的，任意阶的随机响应形式主义。这种修改后的随机动力学特性使相关的多参考电子系统的精确响应特性可以系统地收敛到传统精确处理无法达到的系统上。这要求响应状态与零阶状态同时同步演化，这被证明是稳定的，非瞬态的和无偏的。我们将其应用于分子系统的静态偶极极化性，并以此来解决受限和非受限高级耦合簇线性响应结果之间的差异，这是文献中的高精度基准。

更新日期：2018-06-13

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