Ion-pair dissociation dynamics of H2S in the photon energy range 15.26-15.55 eV.
Ion-pair dissociation dynamics of H2S in the photon energy range 15.26-15.55 eV.
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DOI：
10.1021/jp108808w
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发表时间：
2011-03
期刊：
影响因子：
--
通讯作者：
Shu-Lin Gao;Y. Mo
中科院分区：
文献类型：
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作者：
Shu-Lin Gao;Y. Mo
分别在激发能 15.259、15.395 和 15.547 eV 下测量了 H(2)S + hν → SH(-)(X(1)Σ(+), υ = 0, 1) + H(+) 离子对解离的 H(+) 速度图图像。实验结果表明，大部分可用能量都转化为平动能。碎片 SH(-)(X(1)Σ(+), υ = 0) 的角分布表明解离是通过纯平行跃迁发生的，各向异性参数限制为 +2。由于离子对解离通常通过里德伯态的预解离发生，这表明激发的里德伯态的离子核心具有线性几何形状。采用CASPT2/avqz水平的量子化学计算方法计算了线性H(2)S(+)的几何结构和电子结构。离子对态的电子结构已在CASSCF/avtz水平上计算，这表明离子对态的平衡几何形状具有弯曲的几何形状。
The H(+) velocity map images from the ion-pair dissociation of H(2)S + hν → SH(-)(X(1)Σ(+), υ = 0, 1) + H(+) have been measured at the excitation energies 15.259, 15.395, and 15.547 eV, respectively. The experimental results show that most of the available energies are transformed into the translational energies. The angular distributions of the fragments SH(-)(X(1)Σ(+), υ = 0) indicate that the dissociation occurs via pure parallel transition with limiting anisotropy parameter of +2. Because the ion-pair dissociation usually occurs via the predissociation of Rydberg states, this suggests that the ion cores of the excited Rydberg states have linear geometries. The geometries and electronic structures of the linear H(2)S(+) have been calculated employing the quantum chemistry calculation method at the CASPT2/avqz level. The electronic structures for the ion-pair states have been calculated at the CASSCF/avtz level, which indicates that the equilibrium geometries of the ion-pair states have bent geometries.