4.4 Article

Appropriate description of intermolecular interactions in the methane hydrates: An assessment of DFT methods

期刊

JOURNAL OF COMPUTATIONAL CHEMISTRY
卷 34, 期 2, 页码 121-131

出版社

WILEY
DOI: 10.1002/jcc.23112

关键词

methane hydrate; noncovalent interaction; density functional calculations; ab initio calculations

资金

  1. National Natural Science Foundation of China [11174045]
  2. Fundamental Research Funds for the Central Universities of China [DUT12YQ05]
  3. NSF [EPS-1010094]
  4. Department of Defense [W911NF-12-1-0083]

向作者/读者索取更多资源

Accurate description of hydrogen-bonding energies between water molecules and van der Waals interactions between guest molecules and host water cages is crucial for study of methane hydrates (MHs). Using high-level ab initio MP2 and CCSD(T) results as the reference, we carefully assessed the performance of a variety of exchangecorrelation functionals and various basis sets in describing the noncovalent interactions in MH. The functionals under investigation include the conventional GGA, meta-GGA, and hybrid functionals (PBE, PW91, TPSS, TPSSh, B3LYP, and X3LYP), long-range corrected functionals (omega B97X, omega B97, LC-omega PBE, CAM-B3LYP, and LC-TPSS), the newly developed Minnesota class functionals (M06-L, M06-HF, M06, and M06-2X), and the dispersion-corrected density functional theory (DFT) (DFT-D) methods (B97-D, omega B97X-D, PBE-TS, PBE-Grimme, and PW91-OBS). We found that the conventional functionals are not suitable for MH, notably, the widely used B3LYP functional even predicts repulsive interaction between CH4 and (H2O)6 cluster. M06-2X is the best among the M06-Class functionals. The omega B97X-D outperforms the other DFT-D methods and is recommended for accurate first-principles calculations of MH. B97-D is also acceptable as a compromise of computational cost and precision. Considering both accuracy and efficiency, B97-D, omega B97X-D, and M06-2X functional with 6-311++G(2d,2p) basis set without basis set superposition error (BSSE) correction are recommended. Though a fairly large basis set (e.g., aug-cc-pVTZ) and BSSE correction are necessary for a reliable MP2 calculation, DFT methods are less sensitive to the basis set and BSSE correction if the basis set is sufficient (e.g., 6-311++G(2d,2p)). These assessments provide useful guidance for choosing appropriate methodology of first-principles simulation of MH and related systems. (c) 2012 Wiley Periodicals, Inc.

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