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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structural investigation of asymmetrical dimer radical cation system (H2O-H2S)(+): Proton-transferred or hemi-bonded?
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Structural investigation of asymmetrical dimer radical cation system (H2O-H2S)(+): Proton-transferred or hemi-bonded?

机译：非对称二聚体自由基阳离子体系（H2O-H2S）（+）的结构研究：质子转移还是半键？

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Ab initio molecular orbital and hybrid density functional methods have been employed to characterize the structure and bonding of (H2O-H2S)(+), an asymmetrical dimer radical cation system. A comparison has been made between the two-center three-electron (2c-3e) hemi-bonded system and the proton-transferred hydrogen-bonded systems of (H2O-H2S)(+). Geometry optimization of these systems was carried out using unrestricted Hartree Fock (HF), density functional theory with different functionals, and second-order Moller-Plesset perturbation (MP2) methods with 6-311++G(d,p) basis set. Hessian calculations have been done at the same level to check the nature of the equilibrium geometry. Energy data were further improved by calculating basis set superposition error for the structures optimized through MP2/6-311++G(d,p) calculations. The calculated results show that the dimer radical cation structure with H2O as proton acceptor is more stable than those structures in which H2O acts as a proton donor or the 2c-3e hemi-bonded (H(2)O4SH(2))(+) system. This stability trend has been further confirmed by more accurate G3, G3B3, and CCSD(T) methods. On the basis of the present calculated results, the structure of H4OS+ can best be described as a hydrogen-bonded complex of H3O+ and SH with H2O as a proton acceptor. It is in contrast to the structure of neutral (H2O center dot center dot center dot H2S) dimer where H2O acts as a proton donor. The present work has been able to resolve the ambiguity in the nature of bonding between H2O and H2S in (H2O-H2S)(+) asymmetrical dimer radical cation.
机译：从头算分子轨道和杂种密度函数方法已用于表征（H2O-H2S）（+），一种不对称的二聚体自由基阳离子系统的结构和键。在两个中心的三电子（2c-3e）半键系统与（H2O-H2S）（+）的质子转移氢键系统之间进行了比较。这些系统的几何优化是使用无限制的Hartree Fock（HF），具有不同功能的密度泛函理论以及具有6-311 ++ G（d，p）基集的二阶Moller-Plesset摄动（MP2）方法进行的。已经在相同级别上进行了Hessian计算，以检查平衡几何的性质。通过计算通过MP2 / 6-311 ++ G（d，p）计算优化的结构的基集叠加误差，进一步改善了能量数据。计算结果表明，以水为质子受体的二聚体自由基阳离子结构比以水为质子供体或2c-3e半键合（H（2）O4SH（2））（+）的结构更稳定。系统。更稳定的G3，G3B3和CCSD（T）方法进一步证实了这种稳定性趋势。根据目前的计算结果，H4OS +的结构可以最好地描述为H3O +和SH与氢作为质子受体的氢键复合物。这与中性（H 2 O中心点中心点中心点中心点H 2 S）二聚体的结构相反，其中H 2 O充当质子供体。目前的工作已经能够解决在（H2O-H2S）（+）不对称二聚体自由基阳离子中H2O和H2S之间键合性质的歧义。

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