论文标题
从头算电子结构和形成超速钙的前景 - 金属原子分子离子
Ab initio electronic structure and prospects for the formation of ultracold calcium--alkali-metal-atom molecular ions
论文作者
论文摘要
冷离子原子混合物的实验最近为超速分子离子的生产和应用开辟了道路。在这里，在一项比较研究中，我们从理论上研究了地面和几个激发电子状态，以及形成由钙离子和碱金属原子组成的分子离子的前景：caalk $^{+} $（alk = li，na，na，k，k，rb，cs）。我们使用基于非经验伪能力，操作核心价相关性，较大的高斯基集和价电子的完整构型相互作用方法的量子化学方法。确定并分析了地面和激发电子状态的绝热势能曲线，光谱常数以及过渡和永久性电偶极矩。我们检查了通过自发辐射缔合和激光诱导的光关联来检查离子中性反应过程的前景以及分子离子的产生。之后，计算自发和刺激的黑体辐射过渡速率，并用于获得地面振动状态和第一激发电子状态的辐射寿命。目前的结果为在冷离子原子混合物的现代实验中的钙 - 金属原子离子的形成和光谱铺平了道路。
Experiments with cold ion-atom mixtures have recently opened the way for the production and application of ultracold molecular ions. Here, in a comparative study, we theoretically investigate ground and several excited electronic states and prospects for the formation of molecular ions composed of a calcium ion and an alkali-metal atom: CaAlk$^{+}$ (Alk=Li, Na, K, Rb, Cs). We use a quantum chemistry approach based on non-empirical pseudopotential, operatorial core-valence correlation, large Gaussian basis sets, and full configuration interaction method for valence electrons. Adiabatic potential energy curves, spectroscopic constants, and transition and permanent electric dipole moments are determined and analyzed for the ground and excited electronic states. We examine the prospects for ion-neutral reactive processes and the production of molecular ions via spontaneous radiative association and laser-induced photoassociation. After that, spontaneous and stimulated blackbody radiation transition rates are calculated and used to obtain radiative lifetimes of vibrational states of the ground and first-excited electronic states. The present results pave the way for the formation and spectroscopy of calcium--alkali-metal-atom molecular ions in modern experiments with cold ion-atom mixtures.
