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Concerted Pair Motion Due to Double Hydrogen Bonding: The Formic Acid Dimer Case
Journal of the Indian Institute of Science ( IF 2.3 ) Pub Date : 2019-11-22 , DOI: 10.1007/s41745-019-00137-5
Arman Nejad , Martin A. Suhm

Formic acid dimer as the prototypical doubly hydrogen-bonded gas-phase species is discussed from the perspective of the three translational and the three rotational degrees of freedom which are lost when two formic acid molecules form a stable complex. The experimental characterisation of these strongly hindered translations and rotations is reviewed, as are attempts to describe the associated fundamental vibrations, their combinations, and their thermal shifts by different electronic structure calculations and vibrational models. A remarkable match is confirmed for the combination of a CCSD(T)-level harmonic treatment and an MP2-level anharmonic VPT2 correction. Qualitatively correct thermal shifts of the vibrational spectra can be obtained from classical molecular dynamics in CCSD(T)-quality force fields. A detailed analysis suggests that this agreement between experiment and composite theoretical treatment is not strongly affected by fortuitous error cancellation but fully converged variational treatments of the six pair or intermolecular modes and their overtones and combinations in this model system would be welcome.

中文翻译:

双氢键引起的协同运动:甲酸二聚体案例

从两个甲酸分子形成稳定络合物时失去的三个平移自由度和三个旋转自由度的角度讨论了甲酸二聚体作为典型的双氢键气相物种。回顾了这些强受阻平移和旋转的实验表征,以及尝试通过不同的电子结构计算和振动模型来描述相关的基本振动、它们的组合和它们的热位移。CCSD(T) 级谐波处理和 MP2 级非谐波 VPT2 校正的组合得到了显着的匹配。可以从 CCSD(T) 质量力场中的经典分子动力学中获得振动光谱的定性正确的热位移。
更新日期:2019-11-22
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