Bubin Sergiy, Bednarz Eugeniusz, Adamowicz Ludwik
Department of Physics, University of Arizona, Tucson, AZ 85721, USA.
J Chem Phys. 2005 Jan 22;122(4):41102. doi: 10.1063/1.1850905.
Expanding the wave functions of the ground and excited states of HD(+) (or pde) in terms of spherically symmetric explicitly correlated Gaussian functions with preexponential multipliers consisting of powers of the internuclear distance, and using the variational method, we performed very accurate nonadiabatic calculations of all bound states of this system corresponding to the zero total angular momentum quantum number (vibrational states; v=0-22). The total and the transition energies obtained agree with the best available calculations. For each state we computed the expectation values of the d-p, d-e, and p-e interparticle distances. This is the first time these quantities were computed for HD(+) using rigorous nonadiabatic wave functions. While up to the v=20 state some asymmetry is showing in the d-e and p-e distances, for v=21 and v=22 we observe a complete breakdown of the Born-Oppenheimer approximation and localization of the electron almost entirely at the deuteron.
通过用包含核间距幂次的预指数乘数的球对称显式相关高斯函数展开HD(+)（或pde）基态和激发态的波函数，并使用变分法，我们对该系统对应于总角动量量子数为零（振动态；v = 0 - 22）的所有束缚态进行了非常精确的非绝热计算。得到的总能量和跃迁能量与现有的最佳计算结果一致。对于每个态，我们计算了d - p、d - e和p - e粒子间距离的期望值。这是首次使用严格的非绝热波函数对HD(+)的这些量进行计算。虽然直到v = 20态，d - e和p - e距离显示出一些不对称性，但对于v = 21和v = 22，我们观察到玻恩 - 奥本海默近似完全失效，并且电子几乎完全定域在氘核上。
