National and Kapodistrian University of Athens, Department of Chemistry, Laboratory of Physical Chemistry, Panepistimiopolis - Athens 15771, Hellas.
J Chem Phys. 2011 Oct 7;135(13):134302. doi: 10.1063/1.3643380.
The Ti(2) and Ti(2)(+) molecular systems have been studied through multireference variational and single reference coupled-cluster methods coupled with large basis sets. Potential energy curves have been constructed for 30 (Ti(2)) and 2 (Ti(2)(+)) states and the usual spectroscopic parameters have been extracted. The main feature of the potential curves is the existence of van der Waals minima (Ti(2)) around 7 bohr irrespective of the molecular symmetry, and 4s(2)-4s(1) interactions (Ti(2)(+)) around 6 bohr. Numerous avoided crossings lead to stronger covalent bonds emanating from 4s(1)-4s(1) atomic distributions. The X-state of the neutral species is formally a (3)Δ(g) state with the first excited state lying within 1 kcal/mol. The removal of the symmetry defining e(-) leads to the X(2)Σ(g)(+) state of Ti(2)(+).
通过多参考变分和单参考耦合簇方法与大基组相结合，研究了 Ti(2) 和 Ti(2)(+) 分子体系。构建了 30 个 (Ti(2)) 和 2 个 (Ti(2)(+)) 态的势能曲线，并提取了常用的光谱参数。势能曲线的主要特征是存在范德华最小值 (Ti(2))，约 7 个玻尔，与分子对称性无关，以及 4s(2)-4s(1) 相互作用 (Ti(2)(+))，约 6 个玻尔。许多避免交叉导致更强的共价键源自 4s(1)-4s(1)原子分布。中性物种的 X 态形式上是一个 (3)Δ(g) 态，第一激发态在 1 kcal/mol 以内。去除定义 e(-) 的对称性导致 Ti(2)(+) 的 X(2)Σ(g)(+) 态。
