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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >An ab Initio Study of Linear XH-HX Hydrogen Halide Anions
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An ab Initio Study of Linear XH-HX Hydrogen Halide Anions

机译：线性XH-HX卤化氢阴离子的从头算研究

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This paper examines the stabilities of singly charged anions with the linear opposed dipole structures: FH-HF, ClH-HCl and BrH-HBr at MP2 and CCSD(T) levels. With 6-311+G(3df,2p) basis sets on Cl and Br and aug-cc-pvdz on H and F, MP2 structures were obtained for all three systems. Since the neutral dimers with opposed dipoles are unstable, the energies for the electron detachment processes were evaluated relative to separated free neutrals, viz.: XH-HX·~- → e~- + 2HX. At the CCSD(T) level these energies were 0.26 and 0.84 V for HCl and HBr, respectively, but the value for HF is negative. The addition of diffuse orbitals at the central point between the two H atoms lowered the energy and caused the H-H distance in the FH-HF species to increase. Also the excess electron moved into the diffuse orbitals and the species assumed a solvated electron structure, a finding which is in agreement with previous work. In contrast, for the HCl and HBr species the addition of diffuse orbitals had no significant effect. The optimized geometries, charge and spin distributions, and the adiabatic electron detachment energies all remained essentially unchanged. This result and other molecular parameters indicated that in the ClH-HCl and BrH-HBr anions the extra electrons were located in valence orbitals made up from the σ~* orbitals of the two HX molecules. The nature of these orbitals was discussed. Since the dipole moment of the HCl.HCl neutral dimer is considered too small for formation of a dipole-bound anion state (as occurs with HF.HF), it is quite probable that HCl dimer anion observed experimentally is of the XH-HX·~- type.
机译：本文研究了具有线性相对偶极结构的单电荷阴离子的稳定性：FH-HF，ClH-HCl和BrH-HBr在MP2和CCSD（T）水平下的稳定性。在Cl和Br上具有6-311 + G（3df，2p）基集，在H和F上具有aug-cc-pvdz，对于这三个系统均获得了MP2结构。由于带有相对偶极子的中性二聚体是不稳定的，因此，相对于分离的自由中性，评估了电子分离过程的能量，即：XH-HX·〜-→e〜-+ 2HX。在CCSD（T）等级下，HCl和HBr的能量分别为0.26和0.84 V，但是HF的值为负。在两个H原子之间的中心点添加扩散轨道会降低能量，并导致FH-HF物种中的H-H距离增加。同样，多余的电子也进入了扩散轨道，并且这些物质呈现出溶剂化的电子结构，这一发现与先前的研究相符。相反，对于HCl和HBr物质，添加扩散轨道没有明显影响。优化的几何形状，电荷和自旋分布以及绝热电子脱离能都基本上保持不变。该结果和其他分子参数表明，在ClH-HCl和BrH-HBr阴离子中，多余的电子位于由两个HX分子的σ〜*轨道组成的价态轨道中。讨论了这些轨道的性质。由于HCl.HCl中性二聚体的偶极矩被认为太小而不能形成偶极结合的阴离子状态（如HF.HF所发生的），因此实验观察到的HCl二聚体阴离子很可能是XH-HX· 〜-类型。

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