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首页> 外文期刊>The Journal of Chemical Physics >Mixed time slicing in path integral simulations
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Mixed time slicing in path integral simulations

机译:路径积分模拟中的混合时间切片

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摘要

A simple and efficient scheme is presented for using different time slices for different degrees of freedom in path integral calculations. This method bridges the gap between full quantization and the standard mixed quantum-classical (MQC) scheme and, therefore, still provides quantum mechanical effects in the less-quantized variables. Underlying the algorithm is the notion that time slices (beads) may be collapsed in a manner that preserves quantization in the less quantum mechanical degrees of freedom. The method is shown to be analogous to multiple-time step integration techniques in classical molecular dynamics. The algorithm and its associated error are demonstrated on model systems containing coupled high- and low-frequency modes; results indicate that convergence of quantum mechanical observables can be achieved with disparate bead numbers in the different modes. Cost estimates indicate that this procedure, much like the MQC method, is most efficient for only a relatively few quantum mechanical degrees of freedom, such as proton transfer. In this regime, however, the cost of a fully quantum mechanical simulation is determined by the quantization of the least quantum mechanical degrees of freedom.
机译:提出了一种简单有效的方案,在路径积分计算中将不同的时间片用于不同的自由度。该方法弥合了全量化与标准混合量子经典(MQC)方案之间的差距,因此,仍可在较少量化的变量中提供量子力学效果。该算法的基本概念是,可以以较少的量子机械自由度保留量化的方式折叠时间片(珠子)。该方法与经典分子动力学中的多次积分方法相似。在包含耦合的高频和低频模式的模型系统上演示了该算法及其相关的误差。结果表明,在不同模式下,不同的磁珠数可以实现量子力学可观物的收敛。成本估算表明,此过程非常类似于MQC方法,仅对于相对较少的量子机械自由度(例如质子转移)最有效。但是,在这种情况下,完全量子力学模拟的成本由最小量子力学自由度的量化确定。

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