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中国物理学会期刊

CrHn(n=0,+1,+2)分子及离子的势能函数

CSTR: 32037.14.aps.55.6302

Potentional energy function of CrHn(n=0,+1,+2)

CSTR: 32037.14.aps.55.6302
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  • 用原子分子反应静力学原理推导出CrHn(n=0,+1,+2)的电子状态及其离解极限. 对H原子采用6-311++G**基组,对Cr原子采用SVP(split valence polarization)全电子基组,用B3PW91方法计算了它们的平衡几何、电子状态,在此基础上分别计算CrH,CrH+的Murrell-Sorbie解析势能函数和CrH2+的解析势能函数及其对应的力常数、光谱参数,理论计算值与实验值和文献计算值符合较好. 从离解极限和通道解释了不同的势能函数形状. 计算表明:CrH+的势能曲线均具有对应于稳定平衡结构的极小点,说明CrH+可稳定存在. 而CrH2+离子的势能曲线对应于不稳定的排斥态,说明CrH2+是不稳定的.

     

    Based on the atomic and molecular reaction statics, the ground electronic states of CrH(X6Σ+), CrH+(5Σ+), CrH2+ (6Σ+) and their dissociation limits have been derived. Using density functional method (B3PW91), 6-311++G** basis sets for H and split valence polarization basis sets for Cr, the molecular equilibrium geometry and dissociation energies for CrH+(5Σ+) and CrH2+ (6Σ+) have been calculated. The analytical potential energy functions for CrH(X6Σ+), CrH+(5Σ+) and CrH2+ (6Σ+) are determined. The force fields and spectroscopic parameters have been worked out from these analytical potential energy functions. For the ground state of CrH+, the calculated results of Re, f2, f3, f4, Be, αe, ωe and ωeχe are 0.16200 nm, 1.52574 aJ/nm2, -7.81171 aJ/nm3, 28.61613 aJ/nm4, 6.71181, 0.28792, 1624.6297 and 53.55394 cm-1, respectively; and for the ground state of CrH2+, the corresponding parameters are 0.24005 nm, 0.42946 aJ/nm2, -0.97766 aJ/nm3, 2.40438 aJ/nm4, 2.9562, 0.050184, 858.059 and 6.46813 cm-1, respectively. The theoretical results show minimum points in the potential energy curves of CrH+(5Σ+) and CrH(X6Σ+), so we conclude that CrH(X6Σ+) and CrH+(5Σ+) are stable.But there are no minimum points in the potential energy curves of CrH2+ (6Σ+), so CrH2+ (6Σ+) is not stable.

     

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