Alexandrova Anastassia N, Boldyrev Alexander I, Fu You-Jun, Yang Xin, Wang Xue-Bin, Wang Lai-Sheng
Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300, USA.
J Chem Phys. 2004 Sep 22;121(12):5709-19. doi: 10.1063/1.1783276.
The application of the ab initio genetic algorithm with an embedded gradient has been carried out for the elucidation of global minimum structures of a series of anionic sodium chloride clusters, Na(x)Cl(x+1) (-) (x=1-4), produced in the gas phase using electrospray ionization and studied by photoelectron spectroscopy. These are all superhalogen species with extremely high electron binding energies. The vertical electron detachment energies for Na(x)Cl(x+1) (-) were measured to be 5.6, 6.46, 6.3, and 7.0 eV, for x=1-4, respectively. Our ab initio gradient embedded genetic algorithm program detected the linear global minima for NaCl(2) (-) and Na(2)Cl(3) (-) and three-dimensional structures for the larger species. Na(3)Cl(4) (-) was found to have C(3v) symmetry, which can be viewed as a Na(4)Cl(4) cube missing a corner Na(+) cation, whereas Na(4)Cl(5) (-) was found to have C(4v) symmetry, close to a 3x3 planar structure. Excellent agreement between the theoretically calculated and the experimental spectra was observed, confirming the obtained structures and demonstrating the power of the developed genetic algorithm technique.
从头算遗传算法与嵌入式梯度的应用已被用于阐明一系列气相中通过电喷雾电离产生并通过光电子能谱研究的阴离子氯化钠簇Na(x)Cl(x + 1)(-)（x = 1 - 4）的全局最小结构。这些都是具有极高电子结合能的超卤素物种。对于x = 1 - 4，Na(x)Cl(x + 1)(-)的垂直电子脱离能分别测量为5.6、6.46、6.3和7.0 eV。我们的从头算梯度嵌入式遗传算法程序检测到了NaCl(2)(-)和Na(2)Cl(3)(-)的线性全局最小值以及较大物种的三维结构。发现Na(3)Cl(4)(-)具有C(3v)对称性，可视为缺少一个角部Na(+)阳离子的Na(4)Cl(4)立方体，而发现Na(4)Cl(5)(-)具有C(4v)对称性，接近3×3平面结构。观察到理论计算光谱与实验光谱之间具有出色的一致性，证实了所获得的结构并证明了所开发遗传算法技术的强大功能。
