论文标题
从头开始的元元学习确定超质银簇中温度依赖的自由化景观
Ab initio metadynamics determination of temperature-dependent free-energy landscape in ultrasmall silver clusters
论文作者
论文摘要
从头算元动力学使提取具有第一原理电子结构方法准确性的自由能景观。我们在羽式代码之间介绍了一个接口,该代码计算自由化的景观和增强的采样算法和ASE模块,其中包括几个从头开始的电子结构代码。该界面通过Lennard-Jones群集自由能景观计算验证,通过平均多个短元轨迹轨迹。我们使用此界面和分析将Ag5和Ag6簇的自由化景观估计为10、100和300 K,而回旋和协调数的半径为集体变量,最多发现MEV的大多数误差。两个簇的平面异构体和非平面异构体之间的相对自由能差异随温度而降低,这与先前提出的非平面异构体的稳定相一致。有趣的是,我们发现AG6是最小的银簇,在室温下的熵效应将非平面异构体概率提高到竞争状态。新的ASE填充界面可以在更现实的温度依赖性条件下模拟纳米系统电子性质。
Ab initio metadynamics enables extracting free-energy landscapes having the accuracy of first principles electronic structure methods. We introduce an interface between the PLUMED code that computes free-energy landscapes and enhanced-sampling algorithms and the ASE module, which includes several ab initio electronic structure codes. The interface is validated with a Lennard-Jones cluster free-energy landscape calculation by averaging multiple short metadynamics trajectories. We use this interface and analysis to estimate the free-energy landscape of Ag5 and Ag6 clusters at 10, 100 and 300 K with the radius of gyration and coordination number as collective variables, finding at most tens of meV in error. Relative free-energy differences between the planar and non-planar isomers of both clusters decrease with temperature, in agreement with previously proposed stabilization of non-planar isomers. Interestingly, we find that Ag6 is the smallest silver cluster where entropic effects at room temperature boost the non planar isomer probability to a competing state. The new ASE-PLUMED interface enables simulating nanosystem electronic properties at more realistic temperature-dependent conditions.