Collaborative research: Applicability limits of aqueous pKa values for bulk and surface nanoparticle processes

该奖项由化学部的环境化学科学计划支持。这项合作研究涉及加州大学滨江分校的Kelley Barsanti教授和Bryan Wong教授以及加州大学欧文分校的James Smith教授。他们与研究生和本科生一起研究大气气溶胶（大气中非常细小的液滴）的酸度。导致小颗粒在大气中形成和增长的几个关键过程受到气溶胶颗粒表面和内部酸性的控制。这些小颗粒在大气中的形成和增长对它们对健康的影响以及它们直接和间接影响气候的潜力都有影响。大气气溶胶是直径通常小于100纳米的颗粒。典型的酸性描述不能充分代表这些颗粒中的酸碱化学，因为它们太小了。 该项目旨在了解酸度测量（这里是酸解离常数（pKa））在描述100纳米以下颗粒中酸和碱的行为时的适用性限制。作为长期的本科生暑期实习计划的一部分，研究人员使用AVOGADRO程序进行实时演示，该程序提供了一个易于使用的图形用户界面来创建酸碱分子系统，并执行与该项目相关的初步低水平模拟。因此，该项目提供的实时演示可能对提高少数民族人口对计算引导实验的认识产生重大影响，可能导致更多的少数民族学生寻求环境化学科学的职业生涯。（pKa和pKb），特别是关于亚100 nm颗粒内和颗粒上的酸碱化学。在该尺寸范围内，在CLOUD室进行的直接组成和间接吸湿性测量表明，在过量碱（胺和氨）存在下由硫酸形成的纳米颗粒比使用热力学模型预测的酸性更强。 此外，酸度似乎随粒度从约10 nm（最酸性）到50 nm（更中性）而变化。了解100 nm以下颗粒的酸度对于理解相对简单的酸碱化学非常重要，而且对于准确预测颗粒表面和体相中的酸催化过程也很重要。 该项目的具体目标如下：使用分子建模来预测无机和有机酸和碱的pKa值与颗粒组成和尺寸的函数关系。该活动结合了计算量子化学和分子动力学等技术，以模拟直径高达5 nm的颗粒，并进行实验室实验，以评估预测的pKa值作为组成和大小的函数。这是使用温度和湿度控制的反应室和化学电离质谱仪来确定前体和纳米颗粒的组成。 研究人员还将开发和应用一种适用于大气气溶胶颗粒内部和表面相关过程的多尺度建模的参数化。后一个研究目标可能会导致模型预测能力的提高。这些模型解决了大气中新颗粒形成的机制和物种，以及大气纳米颗粒对人类健康和气候的影响。

This award is supported by the Chemistry Division's Environmental Chemical Sciences Program. The collaborative study involves Professors Kelley Barsanti and Bryan Wong at the University of California, Riverside, and Prof. James Smith at the University of California, Irvine. Together with their graduate and undergraduate students, they investigate the acidity of atmospheric aerosols (very fine droplets in the atmosphere). Several key processes that cause small particles to form and grow in the atmosphere are controlled by the acidity of the surface and interior of aerosol particles. The formation and growth of these small particles in the atmosphere have implications for their effects on health as well as their potential to directly and indirectly impact climate. Atmospheric aerosols are particles that are often smaller than 100 nanometers in diameter. Typical descriptions of acidity fail to adequately represent the acid-base chemistry in these particles because they are so small. This project seeks to understand the limits of the applicability of an acidity measurements (here, acid dissociation constants (pKa)) in describing the behavior of acids and bases in sub-100 nanometer particles. As part of a long-standing summer internship program for undergraduates, the researchers give real-time demonstrations using the AVOGADRO program, which provides an easy-to-use graphical user-interface to create acid-base molecular systems and perform preliminary, low-level simulations relevant to this project. As such, the project provides real-time demonstrations may have a substantial impact in increasing awareness of computationally-guided experiments in underrepresented minority populations, potentially leading to more minority students seeking careers in the environmental chemical sciences.The goal of this research is to determine the limits of applicability for bulk-phase aqueous acid and base dissociation constants (pKa and pKb), particularly as regards acid-base chemistry in and on sub-100 nm particles. In this size range, the direct composition and indirect hygroscopicity measurements performed at the CLOUD chamber show that nanoparticles formed by sulfuric acid in the presence of excess based(amines and ammonia) are more acidic than predicted using thermodynamic models. Further, the acidity appears to vary with particle size from ~10 nm (most acidic) to 50 nm (more neutralized). Knowledge of the acidity of sub-100 nm particles is important for understanding relatively simple acid-base chemistry, but also for accurately predicting acid-catalyzed processes on particle surfaces and in the bulk phase. The specific objectives of this project are as follows: to use molecular modeling to predict pKa values for inorganic and organic acids and bases as a function of particle composition and size. This activity combines techniques such a computational quantum chemistry and molecular dynamics to model particles with diameters of up to 5 nm and to perform laboratory experiments to evaluate the predicted pKa values as a function of composition and size. This is done using a temperature- and humidity-controlled reaction chamber and chemical ionization mass spectrometers to determine precursor and nanoparticle composition. The researchers will also develop and apply a parameterization applicable for multiscale modeling of relevant processes taking place in and on atmospheric aerosol particles. This latter research aim may lead to improvements in the predictive power of models. These models address the mechanisms and species responsible for the formation of new particles in the atmosphere, and the effects of atmospheric nanoparticles on human health and climate.