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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Conical intersection of the ground and first excited states of water: Energies and reduced density matrices from the anti-Hermitian contracted Schr?dinger equation
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Conical intersection of the ground and first excited states of water: Energies and reduced density matrices from the anti-Hermitian contracted Schr?dinger equation

机译：地面与水的第一激发态的圆锥形交点：根据反赫米特收缩的薛定ding方程的能量和密度矩阵

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摘要

A conical intersection between the ground and first-excited states of water is computed through the direct calculation of two-electron reduced density matrices (2-RDMs) from solutions of the anti-Hermitian contracted Schr?dinger equation (ACSE). This study is an extension of a previous study in which the ACSE was used to compute the energies around a conical intersection in the triplet excited states of methylene [Snyder, J. W., Jr.; Rothman, A. E.; Foley, J. J.; Mazziotti, D. A. J. Chem. Phys.2010, 132, 154109]. We compute absolute energies of the 11A′ and 2 1A′ states of water (H2O) and the location of the conical intersection. The ACSE energies are compared to those from ab initio wave function methods. To treat multireference correlation, we seed the ACSE with an initial 2-RDM from a multiconfiguration self-consistent field (MCSCF) calculation. Unlike the situation for methylene, the two states in the vicinity of the conical intersection of water both have the same spatial symmetry. Hence, the study demonstrates the ability of the ACSE to resolve states of the same spatial symmetry that are nearly degenerate in energy. The 2-RDMs from the ACSE nearly satisfy necessary N-representability conditions. Comparison of the results from double-ζ and augmented double-ζ basis sets demonstrates the importance of augmented (or diffuse) functions for determining the location of the conical intersection.
机译：水的基态和第一激发态之间的圆锥形交点是通过根据反赫耳特收缩Schr？dinger方程（ACSE）的解直接计算双电子降密度矩阵（2-RDM）来计算的。这项研究是先前研究的扩展，在该研究中，使用ACSE来计算亚甲基三重激发态中圆锥形交叉点周围的能量[Snyder，J. W.，Jr .; Rothman，A. E .; Foley，J.J .; Mazziotti，D。A. J. Chem。 Phys.2010，132，154109]。我们计算水（H2O）的11A'和2 1A'状态的绝对能量以及圆锥形相交的位置。将ACSE能量与从头算波函数方法得到的能量进行比较。为了处理多参考相关性，我们使用来自多配置自洽字段（MCSCF）计算的初始2-RDM为ACSE注入种子。与亚甲基的情况不同，在水的圆锥形交叉点附近的两个状态都具有相同的空间对称性。因此，该研究证明了ACSE能够解决几乎能量退化的相同空间对称状态的能力。 ACSE的2-RDM几乎满足了必要的N可表示性条件。来自double-ζ和增强的double-ζ基集的结果的比较表明，增强（或扩散）函数对于确定圆锥交点的位置很重要。

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