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A fast approximate extension of the interacting quantum atoms energy decomposition to excited states
Journal of Computational Chemistry ( IF 3 ) Pub Date : 2022-04-26 , DOI: 10.1002/jcc.26863 Jesús Jara-Cortés 1 , Chérif F Matta 2 , Jesús Hernández-Trujillo 3
Journal of Computational Chemistry ( IF 3 ) Pub Date : 2022-04-26 , DOI: 10.1002/jcc.26863 Jesús Jara-Cortés 1 , Chérif F Matta 2 , Jesús Hernández-Trujillo 3
Affiliation
An approach is developed for the fast calculation of the interacting quantum atoms energy decomposition (IQA) from the information contained in the first order reduced density matrix only. The proposed methodology utilizes an approximate exchange-correlation density from Density Matrix Functional Theory without the need to evaluate the correlation-exchange contribution directly. Instead, weight factors are estimated to decompose the exact Vxc into atomic and pairwise contributions. In this way, the sum of the IQA contributions recovers the energy obtained from the electronic structure calculation. This method can, hence, be applied to obtain atomic contributions in excited states on the same footing as in their ground states using any method that delivers the reduced first-order density matrix. In this way, one can locate chromophores from first principles quantum chemical calculations. Test calculations on the ground and excited states of a set of small molecules indicate that the scaled atomic contributions reproduce vertical electronic transition energies calculated exactly. This approach may be useful to extend the applicability of the IQA approach in the study of large photochemical systems especially when the calculations of the second order reduced density matrices is prohibitive or not possible.
中文翻译:
相互作用的量子原子能量分解到激发态的快速近似扩展
开发了一种方法,用于仅从一阶降低密度矩阵中包含的信息快速计算相互作用的量子原子能量分解 (IQA)。所提出的方法利用来自密度矩阵泛函理论的近似交换相关密度,而无需直接评估相关交换贡献。相反,估计权重因子以分解确切的V xc分为原子贡献和成对贡献。通过这种方式,IQA 贡献的总和恢复了从电子结构计算中获得的能量。因此,该方法可用于使用任何提供降低的一阶密度矩阵的方法在与基态相同的基础上获得激发态的原子贡献。通过这种方式,人们可以从第一原理量子化学计算中定位发色团。对一组小分子的基态和激发态的测试计算表明,按比例缩放的原子贡献再现了精确计算的垂直电子跃迁能量。
更新日期:2022-04-26
中文翻译:
相互作用的量子原子能量分解到激发态的快速近似扩展
开发了一种方法,用于仅从一阶降低密度矩阵中包含的信息快速计算相互作用的量子原子能量分解 (IQA)。所提出的方法利用来自密度矩阵泛函理论的近似交换相关密度,而无需直接评估相关交换贡献。相反,估计权重因子以分解确切的V xc分为原子贡献和成对贡献。通过这种方式,IQA 贡献的总和恢复了从电子结构计算中获得的能量。因此,该方法可用于使用任何提供降低的一阶密度矩阵的方法在与基态相同的基础上获得激发态的原子贡献。通过这种方式,人们可以从第一原理量子化学计算中定位发色团。对一组小分子的基态和激发态的测试计算表明,按比例缩放的原子贡献再现了精确计算的垂直电子跃迁能量。