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首页> 外文期刊>Physical Review, A. Atomic, molecular, and optical physics >bled nuclear and electronic ground-state motion from variational reduced-density-matrix theory with applications to molecules with floppy or resonant hydrogens
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bled nuclear and electronic ground-state motion from variational reduced-density-matrix theory with applications to molecules with floppy or resonant hydrogens

机译：变密度密度矩阵理论对核和电子基态运动的影响，并应用于具有软氢或共振氢的分子

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摘要

The variational two-electron reduced-density-matrix (2RDM) method for electronic systems [Phys. Rev. Lett. 93, 213001 (2004)] is extended to compute ground-state distributions of electrons and hydrogen nuclei in molecules beyond the Born-Oppenheimer approximation. While traditional methods for nuclei rely on the construction of expensive potential energy surfaces or other approximations, the variational 2RDM method has the advantage of treating both electrons and hydrogen nuclei as quantum-mechanical particles simultaneously. Because these particles interact by pairwise Coulombic potentials, the ground-state energy is expressible as a linear functional of three 2RDMs corresponding to two electrons, two hydrogens, and one electron and one hydrogen. Nuclei other than hydrogen are treated in the Born-Oppenheimer approximation. Variational optimization of the ground-state energy requires that the 2RDMs be restricted by N-representability conditions to represent a realistic N-particle system where N is the total number of electrons and hydrogens. Recent progress in electronic systems with (i) developing necessary N-representability conditions and (ii) optimizing the ground-state energy subject to these conditions is extended to systems with two types of particles, electrons and nuclei. The nuclear-electronic 2RDM method can be applied to studying macroscopic quantum phenomena in molecules with "floppy" or resonant hydrogens. Illustrative applications are made to (i) large-scale hydrogen motion in hydrogen-bonded molecules and protonated acetylene C_2H_3 + and (ii) hydrogen resonance in malonaldehyde C_3H_4O_2 and ammonia NH3.
机译：电子系统的变分二电子密度降低矩阵（2RDM）方法[Phys。牧师93，213001（2004）]扩展到计算超出Born-Oppenheimer近似的分子中电子和氢核的基态分布。传统的原子核方法依赖于昂贵的势能面或其他近似结构的构造，而变分2RDM方法的优势是可以将电子和氢原子核同时视为量子机械粒子。因为这些粒子通过成对的库仑势相互作用，所以基态能量可以表示为三个2RDM的线性功能，分别对应于两个电子，两个氢，一个电子和一个氢。除氢以外的其他原子核均以Born-Oppenheimer近似值处理。基态能量的变分优化要求2RDM受N可表示性条件的限制，以代表真实的N粒子系统，其中N是电子和氢的总数。 （i）开发必要的N可表示性条件和（ii）在这些条件下优化基态能量的电子系统的最新进展扩展到具有两种类型的粒子（电子和原子核）的系统。核电子2RDM方法可用于研究具有“松散”或共振氢的分子中的宏观量子现象。示例性应用已用于（i）氢键分子和质子化乙炔C_2H_3 +中的大规模氢运动，以及（ii）丙二醛C_3H_4O_2和氨NH3中的氢共振。

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