论文标题
4分量相对论哈密顿量具有有效QED电位的分子计算
4-component relativistic Hamiltonian with effective QED potentials for molecular calculations
论文作者
论文摘要
我们报告了使用狄拉克代码的全电子4组分相对论分子计算的有效QED电位的实施。电势也可用于2组分计算，必须适当的图像变化。从具体而言，我们已经实施了Uehling潜力[E. A. Uehling，物理。 Rev. 48，55（1935）]用于真空极化和两个有效电位[P. Pyykkö和L.-B. Zhao，J。Phys。 B 36，1469（2003）; V. V. Flambaum和J. S. M. Ginges，物理学。 Rev. A 72，052115（2005）]用于电子能源。我们为这些潜力提供广泛的理论背景。我们报告以下样本应用：i）我们确认了Pyykkö的猜想，即通过直接计算MW光谱研究研究的三种同位体的QED效应，可以观察到AUCN分子的QED效应。 QED带来了相应的替代AU -C键长度$ r_s $从0.23至0.04 pm与实验达成协议，ii）van derWaals的光谱常数m $ _2 $ _2 $（m = hg，rn，cn，cn，cn，og）iii）pb $ _2 $ _4 $ _4 $ _4 $ _4 $ _4 $ _ -> pb $ _ -> pb $ _ -> pb y ->因此，如[K. G. Dyall等人，化学。物理。 Lett。 348，497（2001）]。 QED贡献了0.32 kcal/mol的反应能量，从而将其幅度降低-1.27％。对于相应的超重氟烷液体，电子结构非常相似。有趣的是，QED对反应能量的贡献非常相似（0.35 kcal/mol），而相对变化明显较小（-0.50％）。这一奇怪的观察可以通过比正电子自我能量贡献随核电荷的函数更快地增加负真空极化的速度来解释。
We report the implementation of effective QED potentials for all-electron 4-component relativistic molecular calculations using the DIRAC code. The potentials are also available for 2-component calculations, proper picture-change being mandatory. Specificially, we have implemented the Uehling potential [E. A. Uehling, Phys. Rev. 48 , 55 (1935)] for vacuum polarization and two effective potentials [P. Pyykkö and L.-B. Zhao, J. Phys. B 36 , 1469 (2003); V. V. Flambaum and J. S. M. Ginges, Phys. Rev. A 72 , 052115 (2005)] for electron self-energy. We provide extensive theoretical background for these potentials. We report the following sample applications: i) we confirm the conjecture of Pyykkö that QED effects are observable for the AuCN molecule by directly calculating ground-state rotational constants $B_0$ of the three isotopomers studied by MW spectroscopy; QED brings the corresponding substitution Au-C bond length $r_s$ from 0.23 to 0.04 pm agreement with experiment, ii) spectroscopic constants of van der Waals dimers M$_2$ (M=Hg, Rn, Cn, Og) iii) there is a significant change of valence s population of Pb in the reaction PbH$_4$ -> PbH$_2$ + H$_2$, which is thereby a good candidate for observing QED effects in chemical reactions, as proposed in [K. G. Dyall et al., Chem. Phys. Lett. 348 , 497 (2001)]. QED contributes 0.32 kcal/mol to the reaction energy, thereby reducing its magnitude by -1.27 %. For corresponding hydrides of superheavy flerovium, the electronic structures are quite similar. Interestingly, the QED contribution to the reaction energy is of quite similar magnitude (0.35 kcal/mol), whereas the relative change is significantly smaller (-0.50 %). This curious observation can be explained by the faster increase of negative vacuum polarization over positive electron self-energy contributions as a function of nuclear charge.
