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Dispersion Corrections to the Surface Tension at Planar Surfaces

机译:平面表面张力的色散校正

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Molecular dynamics simulations are usually performed using cutoffs (r(c)) for the short-ranged dispersion interactions (r(-6)). For isotropic systems, long-range interactions are often added in a continuum approximation. This usually leads to excellent results that are independent of the cutoff length down to about 1 nm. For systems with interfaces or other anisotropic systems the situation is more complicated. We study here planar interfaces, focusing on the surface tension, which is sensitive to cutoffs. Previous analytic results giving the long-range correction to the surface tension of a liquid-vapor interface as a two- or three-dimensional integral are revisited. They are generalized by introducing a dispersion density profile which makes it possible to handle multicomponent systems. For the simple but common hyperbolic tangent profile the integral may be Taylor-expanded in the dimensionless parameter obtained by dividing the profile width with the cutoff length. This parameter is usually small, and excellent agreement with numerical calculations of the integral is obtained by keeping two terms in the expansion. The results are compared to simulations with different lengths of the cutoff for some simple systems. The surface tension in the simulations varies linearly in r(c)(-2), although a small r(c)(-4)-term may be added to improve the agreement. The slope of the r(c)(-2)-line could in several cases be predicted from the change in dispersion density at the interface. The disagreements observed in some cases when comparing to theory occur when the finite cutoff used in the simulations causes structural differences compared to long-range cutoffs or Ewald summation for the r(-6)-interactions.
机译:分子动力学模拟通常使用截止值(r(c))进行短程分散相互作用(r(-6))。对于各向同性系统,通常以连续近似方式添加远程相互作用。这通常会导致出色的结果,而与截止长度低至约1 nm无关。对于具有接口的系统或其他各向异性系统,情况更为复杂。我们在这里研究平面界面,重点是对截止敏感的表面张力。回顾了先前的分析结果,该分析结果以二维或三维积分形式对液体-蒸汽界面的表面张力进行了长期校正。通过引入分散密度分布来概括它们,从而可以处理多组分系统。对于简单但通用的双曲正切轮廓,积分可以在通过将轮廓宽度除以截止长度而获得的无量纲参数中进行泰勒展开。该参数通常很小,并且通过在展开中保留两个项,可以获得与积分的数值计算的极佳一致性。对于一些简单系统,将结果与具有不同截止长度的仿真进行比较。尽管可以添加一个小的r(c)(-4)项来改善一致性,但模拟中的表面张力在r(c)(-2)中呈线性变化。在某些情况下,r(c)(-2)线的斜率可以通过界面处分散密度的变化来预测。与理论比较时,在某些情况下观察到的分歧发生在模拟中使用的有限截止与r(-6)相互作用的长距离截止或Ewald总和相比导致结构差异时。

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