核-电子关联修正精确波函数分解的分子键指纹
Nucleus-electron correlation revising molecular bonding fingerprints from the exact wavefunction factorization
摘要：
我们提出了一种新的理论和实现计算耦合的电子和量子核子子系统在一个单一的势能面，超越标准的玻恩-奥本海默（BO）分离的原子核和电子。从单产物分子波函数出发，给出了一个精确的自洽核-电子嵌入势，并证明了在离散变量表象中，对于响应于选定原子核的量子非谐振动的平均场电子，可以计算关联核-电子的基本行为.几何规范的选择进行了讨论和必要的制定能量不变的双正交电子方程。我们的方法进一步应用于表征分子能量、键长、质子和电子密度的振动平均分子成键性质。此外，后Hartree-Fock电子关联可以方便地计算的核-电子耦合分子轨道的基础上，证明了二阶Møllet-Plesset微扰和全组态相互作用理论的相关模型。我们的方法不仅精确地量化了非经典的核-电子耦合，用于修正分子成键性质，而且为部署非BO分子量子化学提供了另一种与时间无关的方法。
英文摘要：
We present a novel theory and implementation for computing coupled electronic and quantal nuclear subsystems on a single potential energy surface, moving beyond the standard Born-Oppenheimer (BO) separation of nuclei and electrons. We formulate an exact self-consistent nucleus-electron embedding potential from the single product molecular wavefunction, and demonstrate that the fundamental behavior of correlated nucleus-electron can be computed for mean-field electrons that are responsive to a quantal anharmonic vibration of selected nuclei in a discrete variable representation. Geometric gauge choices are discussed and necessary for formulating energy invariant biorthogonal electronic equations. Our method is further applied to characterize vibrationally averaged molecular bonding properties of molecular energetics, bond length, protonic and electron density. Moreover, post-Hartree-Fock electron correlation can be conveniently computed on the basis of nucleus-electron coupled molecular orbitals, as demonstrated to correlated models of second-order Møllet-Plesset perturbation and full configuration interaction theories. Our approach not only accurately quantifies non-classical nucleus-electron couplings for revising molecular bonding properties, but also provides an alternative time-independent approach for deploying non-BO molecular quantum chemistry.
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