Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, USA.
J Chem Phys. 2011 Sep 28;135(12):124712. doi: 10.1063/1.3633239.
First-principles molecular dynamics simulations, in which the forces are computed from electronic structure calculations, have great potential to provide unique insight into structure, dynamics, electronic properties, and chemistry of interfacial systems that is not available from empirical force fields. The majority of current first-principles simulations are driven by forces derived from density functional theory with generalized gradient approximations to the exchange-correlation energy, which do not capture dispersion interactions. We have carried out first-principles molecular dynamics simulations of air-water interfaces employing a particular generalized gradient approximation to the exchange-correlation functional (BLYP), with and without empirical dispersion corrections. We assess the utility of the dispersion corrections by comparison of a variety of structural, dynamic, and thermodynamic properties of bulk and interfacial water with experimental data, as well as other first-principles and force field-based simulations.
第一性原理分子动力学模拟，其中的力是从电子结构计算中计算出来的，具有提供对界面系统结构、动力学、电子性质和化学的独特见解的巨大潜力，而这是经验力场无法提供的。目前大多数的第一性原理模拟都是由基于密度泛函理论的广义梯度近似的交换相关能量的力驱动的，这种方法无法捕捉色散相互作用。我们已经进行了采用特定的交换相关泛函（BLYP）广义梯度近似的空气-水界面的第一性原理分子动力学模拟，包括和不包括经验色散修正。我们通过与实验数据、其他第一性原理和基于力场的模拟的比较，评估了这些色散修正在各种结构、动力学和热力学性质方面对体相和界面水的有用性。
