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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ion induced dipole clusters H_n~- (3 ≥ n-odd ≥ 13): Density functional theory calculations of structure and energy
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Ion induced dipole clusters H_n~- (3 ≥ n-odd ≥ 13): Density functional theory calculations of structure and energy

机译：离子诱导偶极子簇H_n〜-（3≥n-odd≥13）：结构和能量的密度泛函理论计算

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摘要

We investigate anew the possible equilibrium geometries of ion induced dipole clusters of hydrogen molecular ions, of molecular formula Hn~- (3 ≥ n-odd ≥ 13). Our previous publications [ Sapse, A. M.; et al. Nature 1979, 278, 332; Rayez, J. C.; et al., J. Chem. Phys. 1981, 75, 5393 ] indicated these molecules would have a shallow minimum and adopt symmetrical geometries that accord with the valence shell electron pair repulsion (VSEPR) rules for geometries defined by electron pairs surrounding a central point of attraction. These earlier calculations were all based upon Hartree-Fock (HF) calculations with a fairly small basis of atomic functions, except for the H3- ion for which configuration interaction (CI) calculations were carried out. A related paper [ Hirao, K.; et al., Chem. Phys. 1983, 80, 237 ] carried out similar calculations on the same clusters, finding geometries similar to our earlier calculations. However, although that paper argued that the stabilization energy of negative ion clusters Hn~- is small, vibration frequencies for the whole set of clusters was not reported, and so a definitive assertion of a true equilibrium was not present. In this paper we recalculate the energetics of the ion induced dipole clusters using density function theory (DFT) B3LYP method calculations in a basis of functions (6-311++G(d,p)). By calculating the vibration frequencies of the VSEPR geometries, we prove that in general they are not true minima because not all the resulting frequencies correspond to real values. By searching the energy surface of the B3LYP calculations, we find the true minimum geometries, which are surprising configurations and are perhaps counterintuitive. We calculate the total energy and binding energy of the new geometries. We also calculate the bond paths associated with the quantum theory of atoms in molecules (QTAIM). The B3LYP/6-311++G(d,p) results, for each molecule, deliver bond paths that radiate between each polarized H_2 molecule and the polarizing H~- ion.
机译：我们重新研究了分子式为Hn〜-（3≥n-odd≥13）的氢分子离子的离子诱导偶极簇的可能平衡几何。我们以前的出版物[Sapse，A. M .;等。自然1979，278，332; Rayez，J。C .;等人，化学杂志。物理1981，75，5393]指出这些分子将具有一个最小的最小值，并采用对称的几何构型，该对称构型符合价壳电子对排斥（VSEPR）规则，该规则适用于围绕吸引中心点的电子对所定义的几何构型。这些较早的计算都是基于Hartree-Fock（HF）计算，并具有相当小的原子功能基础，但要进行构型相互作用（CI）计算的H3-离子除外。相关论文[Hirao，K .;等，化学。物理1983，80，237]对相同的星团进行了类似的计算，发现与我们之前的计算相似的几何形状。但是，尽管该论文认为负离子簇Hn〜-的稳定能很小，但并未报告整个簇的振动频率，因此也没有关于真实平衡的明确主张。在本文中，我们在函数（6-311 ++ G（d，p））的基础上，使用密度泛函理论（DFT）B3LYP方法计算重新计算了离子诱导的偶极簇的能量。通过计算VSEPR几何形状的振动频率，我们证明它们通常不是真正的最小值，因为并非所有结果频率都对应于真实值。通过搜索B3LYP计算的能量面，我们找到了真正的最小几何形状，这是令人惊讶的配置，也许是违反直觉的。我们计算新几何的总能量和结合能。我们还计算与分子中原子的量子理论（QTAIM）相关的键路径。对于每个分子，B3LYP / 6-311 ++ G（d，p）结果传递的键合路径在每个极化的H_2分子和极化的H〜-离子之间辐射。

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