Interaction Energy and the Shift in OH Stretch Frequency on Hydrogen Bonding for the H2O→H2O, CH3OH→H2O, and H2O→CH3OH dimers
Interaction Energy and the Shift in OH Stretch Frequency on Hydrogen Bonding for the H2O→H2O, CH3OH→H2O, and H2O→CH3OH dimers
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DOI：
10.1002/jcc.21380
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发表时间：
2010-04-15
影响因子：
3
通讯作者：
Kubicki, James D.
中科院分区：
文献类型：
--
作者：
Campen, Richard Kramer;Kubicki, James D.
利用计算出的OH频率来分配氢键系统中实验观察到的峰值的能力取决于计算的准确性。在这里，我们测试了几种常用的模型化学- hf， MP2和几种与6-31+G(d)和6-311++G（d,p）基集配对的密度泛函-计算H2O -> H2O, CH3OH -> H2O和H2O -> CH3OH二聚体（其中X -> Y， X是氢键供体，Y是受体）的相互作用能（d -c）和OH拉伸基频位移（δ (nu)）的能力。通过与实验和高级计算的比较，我们量化了D-e和delta（nu）中的误差，并使用简单的模式评估了D-e中的误差如何传播到delta（nu）。我们发现B3LYP和MPWB1K在密度泛函方法中表现最好，它们计算δ (nu)的精度接近30-50 cm(-1)，并且在D-c中进行误差校正对于提高计算和实验δ (nu)之间的一致性几乎没有作用。δ (nu)的计算精度也随氢键供体的变化而变化；虽然PBE和TPSS在计算CH3OH -> H2O二聚体的δ (nu)时表现最好，但在描述H2O -> H2O和H2O -> CH3OH时表现相对较差。(C) 2009 Wiley期刊公司计算机学报（英文版）；963 - 972年,2010年
The ability to use calculated OH frequencies to assign experimentally observed peaks in hydrogen bonded system hinges on the accuracy of the calculation. Here we test the ability of several commonly employed model chemistries-HF, MP2, and several density functionals paired with the 6-31+G(d) and 6-311++G(d,p) basis sets-to calculate the interaction energy (D-c) and shift in OH stretch fundamental frequency on dimerization (delta(nu)) for the H2O -> H2O, CH3OH -> H2O, and H2O -> CH3OH dimers (where for X -> Y, X is the hydrogen bond donor and Y the acceptor). We quantify the error in D-e and delta(nu) by comparison to experiment and high level calculation and, using a simple mode, evaluate how error in D-e propagates to delta(nu). We find that B3LYP and MPWB1K perform best of the density functional methods studied, that their accuracy in calculating delta(nu) is approximate to 30-50 cm(-1) and that correcting for error in D-c does little to heighten agreement between the calculated and experimental delta(nu). Accuracy of calculated delta(nu) is also shown to vary as a function of hydrogen bond donor; while the PBE and TPSS functionals perform best in the calculation of delta(nu) for the CH3OH -> H2O dimer their performance is relatively poor in describing H2O -> H2O and H2O -> CH3OH. (C) 2009 Wiley Periodicals, Inc. J Comput Chem 31; 963-972, 2010