摘要翻译:
统计力学的扩展通常被用来从单分子非平衡轨道上所做的功推断自由能。这种方法的一个关键要素是普遍存在的表达式dw/dt=\partial H(x,t)/\partial t,它将随时间变化的力在坐标x上所做的微观功W与在时间t时相应的哈密顿量H(x,t)联系起来。在这里,我们表明,这种联系,尽管是关键的,不能用来估计自由能的变化。我们讨论了这一结果对单分子实验和原子分子模拟的影响,并指出了克服这些限制的可能途径。
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英文标题:
《Failure of the work-Hamiltonian connection for free energy calculations》
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作者:
Jose M. G. Vilar and J. Miguel Rubi
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最新提交年份:
2007
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分类信息:
一级分类:Physics 物理学
二级分类:Statistical Mechanics 统计力学
分类描述:Phase transitions, thermodynamics, field theory, non-equilibrium phenomena, renormalization group and scaling, integrable models, turbulence
相变,热力学,场论,非平衡现象,重整化群和标度,可积模型,湍流
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一级分类:Physics 物理学
二级分类:Soft Condensed Matter 软凝聚态物质
分类描述:Membranes, polymers, liquid crystals, glasses, colloids, granular matter
膜,聚合物,液晶,玻璃,胶体,颗粒物质
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一级分类:Physics 物理学
二级分类:Chemical Physics 化学物理学
分类描述:Experimental, computational, and theoretical physics of atoms, molecules, and clusters - Classical and quantum description of states, processes, and dynamics; spectroscopy, electronic structure, conformations, reactions, interactions, and phases. Chemical thermodynamics. Disperse systems. High pressure chemistry. Solid state chemistry. Surface and interface chemistry.
原子、分子和团簇的实验、计算和理论物理-状态、过程和动力学的经典和量子描述;光谱学,电子结构,构象,反应,相互作用和相。化学热力学。分散系统。高压化学。固态化学。表面和界面化学。
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英文摘要:
Extensions of statistical mechanics are routinely being used to infer free energies from the work performed over single-molecule nonequilibrium trajectories. A key element of this approach is the ubiquitous expression dW/dt=\partial H(x,t)/ \partial t which connects the microscopic work W performed by a time-dependent force on the coordinate x with the corresponding Hamiltonian H(x,t) at time t. Here we show that this connection, as pivotal as it is, cannot be used to estimate free energy changes. We discuss the implications of this result for single-molecule experiments and atomistic molecular simulations and point out possible avenues to overcome these limitations.
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PDF链接:
https://arxiv.org/pdf/704.0761