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首页> 外文期刊>Physical review >Solvent fluctuations and nuclear quantum effects modulate the molecular hyperpolarizability of water
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Solvent fluctuations and nuclear quantum effects modulate the molecular hyperpolarizability of water

机译：溶剂波动和核量子效应调节水的分子超极化性

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摘要

Second-harmonic scattering (SHS) experiments provide a unique approach to probe noncentrosymmetric environments in aqueous media, from bulk solutions to interfaces, living cells, and tissue. A central assumption made in analyzing SHS experiments is that each molecule scatters light according to a constant molecular hyperpolarizability tensor B{2). Here, we investigate the dependence of the molecular hyperpolarizability of water on its environment and internal geometric distortions, in order to test the hypothesis of constant B{2). We use quantum chemistry calculations of the hyperpolarizability of a molecule embedded in point-charge environments obtained from simulations of bulk water. We demonstrate that both the heterogeneity of the solvent configurations and the quantum mechanical fluctuations of the molecular geometry introduce large variations in the nonlinear optical response of water. This finding has the potential to change the way SHS experiments are interpreted: In particular, isotopic differences between H20 and D20 could explain recent SHS observations. Finally, we show that a machine-learning framework can predict accurately the fluctuations of the molecular hyperpolarizability. This model accounts for the microscopic inhomogeneity of the solvent and represents a step towards quantitative modeling of SHS experiments.
机译：次谐波散射（SHS）实验提供了一种独特的方法来探测水性介质中的非中心对称环境，从散装溶液到界面，活细胞和组织。分析SHS实验时做出的主要假设是，每个分子根据恒定的分子超极化率张量B {2）散射光。在这里，我们研究了水的分子超极化性对环境和内部几何畸变的依赖性，以检验常数B {2）的假设。我们使用量子化学计算方法，对通过大量水的模拟获得的点电荷环境中嵌入的分子的超极化性进行了计算。我们证明了溶剂构型的异质性和分子几何结构的量子力学波动都引入了水的非线性光学响应中的大变化。这一发现有可能改变SHS实验的解释方式：特别是H20和D20之间的同位素差异可以解释最近的SHS观测结果。最后，我们证明了机器学习框架可以准确预测分子超极化能力的波动。该模型说明了溶剂的微观不均匀性，代表了对SHS实验进行定量建模的一步。

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  • 来源
    《Physical review》 |2017年第4期|041407.1-041407.6|共6页
  • 作者

    Chungwen Liang; Gabriele Tocci; David M. Wilkins; Andrea Grisafi; Sylvie Roke; Michele Ceriotti;

  • 作者单位

    Laboratory of Computational Science and Modeling, Institute of Materials, Ecole Polytechnique Fdderale de Lausanne,CH-10I5 Lausanne, Switzerland,Laboratory for Fundamental BioPhotonics (LBP), Institute ofBioengineering (IBI), Institute of Materials Science (IMX),School of Engineering (STI), and Lausanne Centre for Ultrafast Science (LACUS), Ecole Polytechnique Federate de Lausanne,CH-1015 Lausanne, Switzerland;

    Laboratory of Computational Science and Modeling, Institute of Materials, Ecole Polytechnique Fdderale de Lausanne,CH-10I5 Lausanne, Switzerland,Laboratory for Fundamental BioPhotonics (LBP), Institute ofBioengineering (IBI), Institute of Materials Science (IMX),School of Engineering (STI), and Lausanne Centre for Ultrafast Science (LACUS), Ecole Polytechnique Federate de Lausanne,CH-1015 Lausanne, Switzerland;

    Laboratory of Computational Science and Modeling, Institute of Materials, Ecole Polytechnique Fdderale de Lausanne,CH-10I5 Lausanne, Switzerland,Laboratory for Fundamental BioPhotonics (LBP), Institute ofBioengineering (IBI), Institute of Materials Science (IMX),School of Engineering (STI), and Lausanne Centre for Ultrafast Science (LACUS), Ecole Polytechnique Federate de Lausanne,CH-1015 Lausanne, Switzerland;

    Laboratory of Computational Science and Modeling, Institute of Materials, Ecole Polytechnique Fdderale de Lausanne,CH-10I5 Lausanne, Switzerland;

    Laboratory for Fundamental BioPhotonics (LBP), Institute ofBioengineering (IBI), Institute of Materials Science (IMX),School of Engineering (STI), and Lausanne Centre for Ultrafast Science (LACUS), Ecole Polytechnique Federate de Lausanne,CH-1015 Lausanne, Switzerland;

    Laboratory of Computational Science and Modeling, Institute of Materials, Ecole Polytechnique Fdderale de Lausanne,CH-10I5 Lausanne, Switzerland;

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