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Can Density Matrix Embedding Theory with the Complete Activate Space Self-Consistent Field Solver Describe Single and Double Bond Breaking in Molecular Systems?
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2018-02-26 00:00:00 , DOI: 10.1021/acs.jctc.7b01248
Hung Q. Pham 1 , Varinia Bernales 1 , Laura Gagliardi 1
Affiliation  

Density matrix embedding theory (DMET) [Phys. Rev. Lett.2012, 109, 186404] has been demonstrated as an efficient wave-function-based embedding method to treat extended systems. Despite its success in many quantum lattice models, the extension of DMET to real chemical systems has been tested only on selected cases. Herein, we introduce the use of the complete active space self-consistent field (CASSCF) method as a correlated impurity solver for DMET, leading to a method called CAS-DMET. We test its performance in describing the dissociation of H–H single bonds in a H10 ring model system and an N═N double bond in azomethane (CH3–N═N–CH3) and pentyldiazene (CH3(CH2)4–N═NH). We find that the performance of CAS-DMET is comparable to CASSCF with different active space choices when single-embedding DMET corresponding to only one embedding problem for the system is used. When multiple embedding problems are used for the system, the CAS-DMET is in good agreement with CASSCF for the geometries around the equilibrium, but not in equal agreement at bond dissociation.

中文翻译:

具有完整激活空间自洽场求解器的密度矩阵嵌入理论能否描述分子系统中的单键和双键断裂?

密度矩阵嵌入理论(DMET)[物理。莱特牧师 2012109,186404]已经证明为有效的基于波函数嵌入方法来治疗的扩展系统。尽管在许多量子晶格模型中取得了成功,但仅在选定的情况下才对DMET扩展到实际化学系统进行了测试。在此,我们介绍使用完整的有源空间自洽场(CASSCF)方法作为DMET的相关杂质求解器,从而产生一种称为CAS-DMET的方法。我们在描述H 10环模型系统中H–H单键和偶氮甲烷(CH 3 –N═N–CH 3)和戊二氮(CH 3(CH)24 –N = NH)。我们发现,当使用仅对应于系统一个嵌入问题的单嵌入DMET时,在不同的活动空间选择下,CAS-DMET的性能可与CASSCF媲美。当系统使用多个嵌入问题时,CAS-DMET与CASSCF在平衡周围的几何形状方面具有很好的一致性,但在键解离时却没有一致性。
更新日期:2018-02-26
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