Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA.
J Chem Phys. 2019 Feb 7;150(5):054501. doi: 10.1063/1.5079735.
When a finite sample of water experiences tension, it may develop voids (bubbles). We present here a result for the work (Helmholtz free energy change) that needs to be done for the creation of a bubble in fixed volume of water under tension and show that this result depends on the general form of stress-strain relationship. We observe that it is very important to include the curvature-dependent surface tension into consideration in order to explain bubble stability. The analytical result we obtained for the free energy allows us to make prediction for the values of critical and stable radii of the bubbles. We also performed simulations on the TIP4P/2005 water model and observed creation of bubbles in water under stretch. Combining analytical results obtained from our thermodynamic description with the results from computer simulations allowed us to determine the two parameters that describe the curvature-dependent surface tension and also to find the values of critical and stable bubble radii. We also determined the values of critical bubble radii by using mean first-passage time calculations.
当有限量的水受到张力时,它可能会形成空隙(气泡)。我们在此介绍一个结果,即在固定体积的受张力的水中形成气泡所需的功(亥姆霍兹自由能变化),并表明该结果取决于一般形式的应力-应变关系。我们观察到,为了解释气泡的稳定性,非常有必要将曲率相关的表面张力纳入考虑。我们获得的自由能分析结果使我们能够对气泡的临界和稳定半径进行预测。我们还在 TIP4P/2005 水模型上进行了模拟,并观察到在拉伸下水中气泡的形成。将我们的热力学描述中获得的分析结果与计算机模拟的结果相结合,使我们能够确定描述曲率相关表面张力的两个参数,并找到临界和稳定气泡半径的值。我们还通过平均首次通过时间计算确定了临界气泡半径的值。