Gutsev G L, Bozhenko K V, Gutsev L G, Utenyshev A N, Aldoshin S M
Department of Physics, Florida A&M University , Tallahassee, Florida 32307, United States.
Institute of Problems of Chemical Physics, Russian Academy of Sciences , Chernogolovka 142432, Moscow Region, Russia.
J Phys Chem A. 2017 Feb 2;121(4):845-854. doi: 10.1021/acs.jpca.6b11036. Epub 2017 Jan 24.
The geometrical and electronic structures of the CrO and CrO clusters are computed using density functional theory with a generalized gradient approximation in the range of 1 ≤ n ≤ 14. Local total spin magnetic moments, polarizabilities, binding energies per atom, and energies of abstraction of O and O are computed for both series along with electron affinities of the neutrals and vertical detachment energies of the anions. In the lowest total energies states of CrO, CrO, CrO, CrO, CrO, CrO, and CrO, total spin magnetic moments of the Cr atoms are quite large and antiferromagnetically coupled. In the rest of the series, at least one of the Cr atoms has no spin-magnetic moment at all. The computed vertical electron-detachment energies of the CrO are in good agreement with experimental values obtained in the 1 ≤ n ≤ 7 range. All neutral CrO possess electron affinities larger than the electron affinities of halogen atoms when n > 6 and are thus superhalogens. It is found that the neutrals and anions are stable with respect to the abstraction of an O atom in the whole range of n considered, whereas both neutrals and anions became unstable toward the loss of O for n > 7. The polarizability per atom decreases sharply when n moves from one to four and then remains nearly constant for larger n values in both series. The largest members in both series, CrO and CrO, possess the geometrical structures of the Cr(O) type by analogy with monochromium Cr(O).
使用密度泛函理论并采用广义梯度近似，在1≤n≤14范围内计算了CrO和CrO团簇的几何结构和电子结构。计算了这两个系列的局部总自旋磁矩、极化率、每个原子的结合能以及O和O的提取能量，同时还计算了中性物的电子亲和能和阴离子的垂直脱附能。在CrO、CrO、CrO、CrO、CrO、CrO和CrO的最低总能量状态下，Cr原子的总自旋磁矩相当大且呈反铁磁耦合。在该系列的其余部分，至少有一个Cr原子根本没有自旋磁矩。计算得到的CrO的垂直电子脱附能与在1≤n≤7范围内获得的实验值吻合良好。当n>6时，所有中性CrO的电子亲和能都大于卤素原子的电子亲和能，因此它们是超卤素。研究发现，在所考虑的整个n范围内，中性物和阴离子对于O原子的提取是稳定的，而当n>7时，中性物和阴离子对于O的损失都变得不稳定。当n从1增加到4时，每个原子的极化率急剧下降，然后在两个系列中对于更大的n值几乎保持不变。两个系列中最大的成员CrO和CrO，类似于单铬Cr(O)，具有Cr(O)类型的几何结构。
