Name: vibrational spectra of a n719-chromophore/titania interface from empirical-potential molecular-dynamics simulation, solvated by a room temperature ionic liquid
Uploaded: 2020-01-25T12:00:00
Description: Watch this Scientific Journal Video about Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liqui

作者感谢大卫·科克教授的有益讨论和爱尔兰科学基金会（SFI）提供高性能计算资源。这项研究得到了由欧洲区域发展基金共同资助的SFI-NSFC双边供资计划（赠款编号SFI/17/NSFC/5229）以及三级机构研究方案（PRTLI）第5周期的支持。

1. 使用DL_POLY执行 MD 仿真
<ol><li>构造DSC系统N719-dye吸附到由[bmim][NTf2]溶解的Anatase-titania表面的初始结构-取自以前的工作12，13。使用 VESTA 软件绘制所需的结构。</li>
	<li>选择N719 cis-di（硫磺）-二（2，2'-bipyridl-4-碳化酸-碳素酸）-二）-敏感染料（II），不产生反离子，并确保存在两个表面结合的质子，以提供整个系统电荷中性。 注：事实上，De A...

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Ab initio 仿真技术执行成本很高，因此，在较长的时间尺度上执行仿真至少需要使用一些 DSC 系统的经验力场。为此，使用经验、经典模拟力场为MD创建了等效的[bmim]=[NTf2]-溶化接口的原子模型。阿他塞是使用松井-Akaogi （MA） 力场建模的，而染料结构则使用 OPLS 参数进行处理。对于 RTIL，采用了四个不同的力场来确定 RTIL 电荷对染料振动动力学的重要性。力场参数各相同，只有电荷?...

在染料敏化太阳能电池（DSC）中，半导体的光带间隙由光吸收或敏化染料桥接。DSC 需要持续充电：因此，氧化还原电解质对于促进这种恒定的电荷供应（通常以 I-/I3-有机溶剂的形式）至关重要。这有利于从敏感染料到电解质的孔的传递，注入光兴奋电子进入金属氧化物基板，通过外部电路，最终重组发生在阴极1。DSC 对各种真实应用的积极前景的一个关键方面源于其直接制造，无需高纯度的原材料;这与硅基光伏所需的高资本成本和超纯度形成鲜明对比。无论如何，通过将不太稳定的电解质与具有低挥发性室温离子液体（RILs）的电解质交换，显著改善DSC的工作寿命时间尺度的前景显示出巨大的前景。RTIL 的固体状物理特性与其液体状电气特性（如低毒性、易燃性和挥发性）1相结合，可构成相当优秀的候选电解质，用于 DSC 应用。
鉴于DSC中RtIL的这种前景，毫不奇怪，近年来，在研究DSC原型N719-色光/钛酸盐与RLT的接口方面，活动有了实质性的提高。特别是，对这类系统进行了重要的工作，其中考虑了一系列广泛的物理化学过程，包括染料2、5中的电荷补充动力学、电子孔动力学和转移3的机械步骤，当然还有钛基板的纳米尺度性质对这些和其他过程4的影响。
现在，牢记基于DFT的分子模拟，特别是AIMD的惊人进展6，作为材料科学中非常有用的原型设计工具，尤其适用于 DSC7,8,9,10,11，对最佳功能选择进行关键评估至关重要8,9，AIMD 技术在研究 DSC 半导体表面的染料结构、吸附模式和振动特性方面，在审查相当显著的分散和显式 RTIL 溶解效应方面已经证明非常有用。特别是，AIMD的采用在取得合理、半定量捕获和预测重要电子特性（如带隙）以及结构结合方面取得了一些成功13和振动光谱14在参考。12-14，AIMD模拟对与（101）阿他拉酶-蒂尼亚表面结合的光活性N719-色磷染料进行了广泛的模拟，评估了两者同时存在的电子特性和结构特性。+[NTf2]-12,13和 [bmim]+[I]-14RtIL，除了[bmim] 的振动光谱外+[I]-14.特别是半导体表面的刚度15，除了其固有的比较光活动外，还导致表面在 AIMD 模拟中略有变化，这使得 （101） anatase 接口12,13,14一个合适的选择。如参考文献12所示，阳离子和表面之间的平均距离下降约0.5°，阳离子和离子之间的平均分离减少0.6°，并且染料周围第一层的RtIL明显改变，阳离子位于aver上年龄1.5°离染料中心更远，是由RTIL-溶解系统中显式分散相互作用直接引起的。吸附N719染料配置的实物扭结也是在真空中引入显式分散效应的结果。在参考文献第13中，对显式RTIL溶解和功能选择对这些结构效应是否影响DSSCs的行为进行了分析，认为显式溶解和分散处理都非常重要。在参考文献第14条中，由于手头有其他组的高质量实验振动光谱数据，对两个显性[bmim]的特定效应进行了系统基准测试。+[I]-解析和正确处理在 refs 中建立的分散。12~13关于显性光谱模式特征的再现;这得出了显式溶解的重要性，同时准确处理分散相互作用，与早期在显性溶剂中催化剂的AIMD建模中的结构和动态特性的发现相呼应16.事实上，Mosconi等人也对DSC仿真的DFT处理的显性解解效果进行了令人印象深刻的评估17.巴赫尔等人18研究染料的实验吸收光谱以及TD-DFT水平的相关光谱;这些TD-DFT光谱在计算转换方面与实验同行非常一致。此外，Preat等人还在几个溶剂中研究了苯丙氨酸（PYR）衍生物的吸收光谱。19，提供对染料的几何和电子结构的重要见解，并证明适当的结构修改，以优化基于 PYR 的 DSSc 的特性 - 一种以模拟为主导/合理化的"分子设计"的精神。
明确确立了DFT和AIMD对DSC特性和功能的精确建模的重要贡献，包括从结构、电子和振动角度明确解构和适当处理分散相互作用等重要技术问题，现在，在目前的工作 - 焦点转向如何调整经验-潜在方法，以解决这种原型DSC系统的结构和振动特性的贴合和合理预测，以N719染料吸附在aatase（101）在[bmim][NTf2]- RTIL作为一个例子的实用问题。这一点很重要，不仅因为可用于更广泛地处理DSC模拟7和金属氧化物表面的基于力场的分子模拟活动和方法学机械，还因为它们相对于基于DFT的方法的计算成本惊人地降低，而且有可能非常高效地耦合偏置采样方法，以更有效地捕获高粘性RRTIL溶剂中的三相空间和结构演化，在环境温度下以固体状的物理特性为主。因此，在DFT和AIMD以及振动光谱14实验数据以及振动光谱14实验数据下，基于这种开放式的测量和优化力场方法问题，我们转向利用N719染料原子速度自相关函数（VACF）的质加权傅立叶变换，从MD评估振动光谱预测中的经验-势能的紧迫任务。一个关键问题是RTIL的不同部分电荷参数化如何影响振动光谱预测，并特别注意这一点，以及相对于实验和AIMD20为最佳光谱模式预测而定制力场的更广泛任务。

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			<td>This was a molecular simulation, so no experimental equipment was used.</td>
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			<td>The name of the software was DL-POLY (the &#39;Classic&#39; version of which is available under GnuPublic Licence, via sourceforge)</td>
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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

光活性金属氧化物表面与光吸收染料接触的振动光谱和其他结构、能量和光谱特性的准确分子模拟预测，是物理化学中一个持续棘手的、难以捉摸的挑战。考虑到这一点，分子动力学 （MD） 模拟是通过使用优化的经验电位，对由广泛研究的室温离子液体 （RTIL） 溶解的具有良好代表性和原型染料敏化的太阳能电池 （DSC） 进行，其伪装为 [bmi]=[NTf2]- RTIL 将 N719 感化染料吸附到 101.在此过程中，我们收集了重要的见解，了解了如何使用 RTIL 作为电解孔接受器调节 N719 染料的动态和振动特性，通过傅立叶从 MD 转换质量加权速度自相关函数来估计 DSC 光活动接口的光谱。将获得的振动光谱与实验光谱和从ab initio分子动力学（AIMD）取样的光谱进行了比较;特别是，从MD生成的各种经验电位光谱提供了对离子液体部分电荷电荷参数化如何影响振动光谱预测的见解。无论如何，经过AIMD和实验验证，仔细安装经验力场模型是处理DSC振动特性的有效工具。

绑定Motif的结构特性 在 MD 的 15 ps 之后，图 2描述了四个不同部分电荷集的代表性绑定图案。在图2a，对于（上述）文献衍生电荷，可以看出与表面质子有突出的氢键相互作用。通过对轨道的仔细分析，氢键大多是表面质子结合的，而另外三个（AIMD衍生的）20个电荷组没有与表面质子...

Watch this Scientific Journal Video about Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liqui

Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid

染料敏化太阳能电池由RTL溶解;利用优化的经验电位，应用分子动力学模拟计算振动特性。将所得振动光谱与实验和abinitio分子动力学进行了比较;各种经验电位光谱显示了离子液体的偏电荷电荷参数化如何影响振动光谱预测。

N719-色光/钛合金界面的振动光谱，来自经验-电位分子动力学模拟，由室温离子液体解低

The accurate molecular simulation prediction of vibrational spectra, and other structural, energetic and spectral characteristics, of photo-active ...

该协议涉及如何调整经验潜力方法，以解决原型染料敏感太阳能电池系统的结构和振动特性的合理预测。这一点很重要，因为计算成本方法的降低惊人，有可能采用各种采样方法。要执行分子动态仿真，请打开DL_POLY模拟软件文件，并使用 Lopez 等人经过验证的力场。通过经验电位放松室温离子液体配置。然后使用松井-阿卡奥吉力场，包括泰坦尼亚在放松过程中的移动性，以模型阿纳塔塞。若要执行结合梯度最小化相对终止梯度为 0.0001 的几何优化，请在字段文件中指定 15 皮秒的优化，在 NVT 组合中，时间停止时间为 300 Kelvin。要运行DL_POLY终端上，请输入DL_POLY。X.In，为 NVT 指定 Nose-Hoover，并选择每飞秒打印一次位置速度轨迹。对于 Anatase 表面，请确保它沿 x 和 y 实验室轴周期性地投射到室温离子液体上，形成一对平行表面，其 x 轴为 21 个焦虑，y 轴为 21 个焦虑。确保具有明确溶剂的染料敏感太阳能电池系统由827个原子组成。对于在气穴的情况下，系统中应该有347个原子。在伦纳德-琼斯参数的字段文件中，应用 Lorentz-Berthelot 组合规则，输入伦纳德-琼斯半径的算术均值和伦纳德-琼斯井深的几何均值，用于非粘结交互选项卡下字段文件底部的经验力字段。要处理远程静电，请使用非粘结截止长度为 10 个焦虑的 Ewald 方法应用 Ewald 方法，并在控制文件中将 Ewald 方法的实际空间衰减参数设置为每非粘结截止长度约 3.14。然后选择 Ewald 波向量的数量，以确保 Ewald 评估中对控制文件中负五乘值的 1 倍 10 的相对容差。使用 REVCON 文件重命名为配置执行一系列潜在能量评估，直到输出中的系统压力收敛到几分之内，以选择非粘结截止长度。从历史文件中，单独使用 Python 硅藻速度。py 在终端中提取每个步骤的单个 x、y 和 z 速度。要计算速度自动关联函数，请使用 vacf151005。py 并classical_dye_autocore。嘘到终端。将计算所有硅藻的速度自动相关函数。要从分子动力学中计算光谱，请使用染料原子速度自动相关函数的质量加权的 Fourier 变换，请使用 Python MWPS。py 并run_all_4。sh 在终端。将计算质量加权功率光谱。要评估室温离子液体中部分变化集，以便英制潜在基分子动态模拟，以便随时相互比较，请准备一个文献费用表，然后在此表中输入 DL-POLY 的字段文件格式。要计算 Mulliken 室温离子液体电荷，平均超过 ab-initio 分子动力学轨迹的四个点，重新规范化并准备文献电荷表，并输入表到 DL-POLY 的字段文件格式。要执行 EHT 分析，平均超过分子操作环境软件包中实现的 ab-initio 分子动力学轨迹的四个点。重新规范化并准备文献费用表，然后将字段输入 DL-POLY 的字段文件格式。在这里，显示了分子动力学15皮秒后四个不同部分电荷集的代表性结合图案。对于所展示的文献推导电荷，可以观察到与表面质子的突出的氢键相互作用。然而，三个ab-initio分子动力学派生电荷集不具有如此强烈的库洛比性相互作用与表面质子。事实上，与从 ab-iitio 分子动力学中通过各种方式采样的部分电荷相比，文献中部分电荷的幅度较小，因此，相对于较大幅度的部分室温离子液体电荷，电荷屏蔽程度较小。有趣的是，Mulliken衍生电荷集显示了染料的某种持续扭结，在甲酸酶表面具有突出的氢键，与桥接氧原子结合。更好的质量电荷适合从 ab-initio 分子动力学导致更现实的 N719 结合图案，符合基于 PEV 的出生-奥本海默分子动力学具有格里姆-D3 分散。质量加权 ab-initio 分子动力学速度自动相关函数光谱结果显示了 300 至 400 厘米区域的光谱峰聚类。经典光谱中存在的主要山峰为文献派生电荷为600厘米和800厘米，Mulliken电荷为525厘米和800厘米，EHT电荷为675厘米、810厘米和900厘米，赫希费尔德电荷为650厘米、800厘米和900厘米。请务必检查 Titania 几何体的所有方向的初始结构。为了优化，可以使用力场来评估振动光谱的实证电位，如分子动力学预测的那样。a-initio分子动力学是一种有效和有前途的策略。分子动力学的使用在模拟中可能也很重要，使染料敏感太阳能电池原型

Research

JoVE Journal

Chemistry

Untargeted Metabolomics from Biological Sources Using Ultraperformance Liquid Chromatography-High Resolution Mass Spectrometry (UPLC-HRMS)

Untargeted Metabolomics from Biological Sources Using Ultraperformance Liquid Chromatography-High Resolution Mass Spectrometry UPLC-HRMS

不相关的代谢组学，生物源使用超高效液相色谱 - 高分辨质谱（UPLC-HRMS）

Here we present a workflow to analyze the metabolic profiles for biological samples of interest including; cells, serum, or tissue. The sample is first ...

科研

化学

Isolation and Preparation of Bacterial Cell Walls for Compositional Analysis by Ultra Performance Liquid Chromatography

通过超性能液相色谱对细菌细胞壁进行隔离和制备，进行组成分析

The bacterial cell wall is critical for the determination of cell shape during growth and division, and maintains the mechanical integrity of cells in the ...

Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

1,6-酮酯高立体选择性合成离子液体介导：三组分反应启用快速进入低分子量胶凝剂的新型类

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form ...

Preparation of Carbon Nanosheets at Room Temperature

碳纳米片在室温下准备

Amphiphilic molecules equipped with a reactive, carbon-rich "oligoyne" segment consisting of conjugated carbon-carbon triple bonds self-assemble into ...

Synthesis and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals

合成与盘状磷酸盐锆剥落获取胶体液晶

Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and ...

Temperature-programmed Deoxygenation of Acetic Acid on Molybdenum Carbide Catalysts

对碳化钼催化合成乙酸的程序升温脱氧

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system ...

From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

从分子到材料: 通过卤素键合工程新的离子液体晶体

Herein, we demonstrate that a bottom-up approach, based on halogen bonding (XB), can be successfully applied for the design of a new type of ionic liquid ...

Total Internal Reflection Absorption Spectroscopy (TIRAS) for the Detection of Solvated Electrons at a Plasma-liquid Interface

Total Internal Reflection Absorption Spectroscopy TIRAS for the Detection of Solvated Electrons at a Plasma-liquid Interface

全内反射吸收光谱法 (拉斯) 在等离子体-液体界面上检测溶剂电子

The total internal reflection absorption spectroscopy (TIRAS) method presented in this article uses an inexpensive diode laser to detect solvated ...

Microfluidic Preparation of Liquid Crystalline Elastomer Actuators

液晶弹性体致动器的微流控制备

This paper focuses on the microfluidic process (and its parameters) to prepare actuating particles from liquid crystalline elastomers. The preparation ...

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

利用密度泛函理论和力场分子动力学对多相水-金属催化剂接口进行多尺度采样

A significant number of heterogeneously-catalyzed chemical processes occur under liquid conditions, but simulating catalyst function under such conditions ...