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Path Between Thermodynamics States01:21

Path Between Thermodynamics States

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Consider the two thermodynamic processes involving an ideal gas that are represented by paths AC and ABC in Figure 1:
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Thermodynamic Potentials01:26

Thermodynamic Potentials

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Thermodynamic potentials are state functions that are extremely useful in analyzing a thermodynamic system. They have dimensions of energy. The four important thermodynamic potentials are internal energy, enthalpy, Helmholtz free energy, and Gibbs free energy. These thermodynamic potentials can be expressed using two of the following variables: pressure, volume, temperature, and entropy. These two variables are expressed as the rate of change of the thermodynamic potential with respect to other...
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Maxwell's Thermodynamic Relations01:23

Maxwell's Thermodynamic Relations

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Maxwell's thermodynamic relations are very useful in solving problems in thermodynamics. Each of Maxwell's relations relates a partial differential between quantities that can be hard to measure experimentally to a partial differential between quantities that can be easily measured. These relations are a set of equations derivable from the symmetry of the second derivatives and the thermodynamic potentials.
All thermodynamic potentials are exact differentials. Therefore, their second-order...
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Maxwell-Boltzmann Distribution: Problem Solving01:20

Maxwell-Boltzmann Distribution: Problem Solving

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Individual molecules in a gas move in random directions, but a gas containing numerous molecules has a predictable distribution of molecular speeds, which is known as the Maxwell-Boltzmann distribution, f(v).
This distribution function f(v) is defined by saying that the expected number N (v1,v2) of particles with speeds between v1 and v2 is given by
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Thermodynamic Systems01:06

Thermodynamic Systems

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A thermodynamic system is a set of objects whose thermodynamic properties are of interest. The system is considered to be embedded in its surroundings or the environment. The system and its environment can exchange heat and do work on each other through a boundary that separates them. However, the immediate surroundings of the system interact with it directly and therefore have a much stronger influence on its behavior and properties.
Consider an example of  tea boiling in a kettle. The...
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Adiabatic Processes for an Ideal Gas01:18

Adiabatic Processes for an Ideal Gas

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When an ideal gas is compressed adiabatically, that is, without adding heat, work is done on it, and its temperature increases. In an adiabatic expansion, the gas does work, and its temperature drops. Adiabatic compressions actually occur in the cylinders of a car, where the compressions of the gas-air mixture take place so quickly that there is no time for the mixture to exchange heat with its environment. Nevertheless, because work is done on the mixture during the compression, its...
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Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
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基准测试各种非adiabatic半古典映射动力学方法与张量列车热场动力学.

Zengkui Liu1,2,3, Ningyi Lyu1,4, Zhubin Hu1,2,5

  • 1Division of Arts and Sciences, NYU Shanghai, 567 West Yangsi Road, Shanghai 200124, China.

The Journal of chemical physics
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概括

基准测试近似量子动力学方法显示,对于非adiabatic过程的最佳方法是系统特定的. 精度取决于零点能量和用于映射变量的初始采样策略.

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科学领域:

  • 量子化学是一种量子化学.
  • 计算物理学的计算物理.
  • 化学动力学 化学动力学

背景情况:

  • 准确的量子动力学模拟对于理解电子转移,能量转移和光化学反应至关重要.
  • 复杂系统中的非adiabatic过程需要可靠的模拟方法.

研究的目的:

  • 将各种近似非adiabatic动力学方法与数值精确的张量列 (TT) 计算进行比较.
  • 评估各种模型系统中不同方法的性能.

主要方法:

  • 对近似方法进行比较 (Ehrenfest,最少开关的表面跳跃,线性化半古典绘图等). 具有精确的TT-KSL和TT热场动态.
  • 使用的模型系统:自旋玻色子,线性振动合,视网膜光异构化和塔利的散射模型.

主要成果:

  • 最佳的近似非亚亚动态动力学方法高度依赖于系统.
  • 精度对零点能量参数和映射变量的初始采样敏感.

结论:

  • 对于所有非adiabatic动态模拟来说,没有一个单一的近似方法是普遍优秀的.
  • 精心选择方法和参数对于可靠的量子动力学研究至关重要.