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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Stability of Hemi-Bonded vs Proton-Transferred Structures of (H_2O)_2~+, (H_2S)_2~+, and (H_2Se)_2~+ Studied with Projected Hartree?Fock Methods
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Stability of Hemi-Bonded vs Proton-Transferred Structures of (H_2O)_2~+, (H_2S)_2~+, and (H_2Se)_2~+ Studied with Projected Hartree?Fock Methods

机译：投影Hartree-Fock方法研究（H_2O）_2〜+，（H_2S）_2〜+和（H_2Se）_2〜+的半键键与质子转移结构的稳定性

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摘要

Hartree?Fock (HF) is known to suffer from drawbacks in the description of the relative stabilities between the hemi-bonded (HB) and proton-transferred (PT) isomers of the water dimer cation, (H_2O)_2~+. The energy difference predicted by HF is too large, approximately 27 kcal/mol, which is lowered to 7 kcal/mol when correlation effects are added. The error in HF has been previously attributed to the large dynamic correlation effects in the HB structure as well to the large symmetry breaking this structure exhibits. In this study we use the recently developed projected Hartree?Fock (PHF) methods to study the relative stability of the two isomers of (H_2O)_2~+ as well as its second and third row analogs, namely, (H_2S)_2~+ and (H_2Se)_2~+. In PHF, symmetries are broken and restored in a variation-afterprojection approach and thus can deal easily with systems for which HF itself spontaneously breaks symmetry. We use different flavors of PHF (SUHF, KSUHF, SGHF, and KSGHF) to explore their ability in capturing dynamic correlation effects and to compare their performance to different wave function based methods. We study the role of the symmetry-breaking in the above systems, using wave function based methods with unrestricted and restricted wave functions as well as performing a single-shot symmetry restoration (a projection-after-variation scheme).
机译：众所周知，Hartree？Fock（HF）在描述水二聚体阳离子（H_2O）_2〜+的半键合（HB）和质子转移（PT）异构体之间的相对稳定性方面存在缺陷。 HF预测的能量差太大，大约为27 kcal / mol，添加相关效应后会降低到7 kcal / mol。 HF中的错误先前已归因于HB结构中的大动态相关效应以及破坏该结构所表现出的大对称性。在这项研究中，我们使用最近开发的投影Hartree？Fock（PHF）方法研究（H_2O）_2〜+的两个异构体以及其第二和第三行类似物（H_2S）_2〜+的相对稳定性。和（H_2Se）_2〜+。在PHF中，对称性会以“投影后变化”的方式被破坏和恢复，因此可以轻松应对HF本身自发地破坏对称性的系统。我们使用不同风味的PHF（SUHF，KSUHF，SGHF和KSGHF）来探索它们捕获动态相关效应的能力，并将其性能与基于不同波函数的方法进行比较。我们使用不受限波函数和受限波函数的基于波函数的方法，以及执行单次对称恢复（变异后投影方案），研究上述系统中对称破坏的作用。

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