Multiconfiguration Pair-Density Functional Theory for Complex Chemical Systems

明尼苏达大学的Laura Gagliardi和Donald G. Truhlar获得了化学学部化学理论、模型和计算方法项目的奖励，他们开发了一种理论，可以对大型系统的化学反应进行高精度计算。这种多构型对密度泛函理论（MC-PDFT）最近被引入，作为一种实用的方法来处理键断裂、电子被激发或含有过渡金属的系统的反应。所有这些例子都涉及到多个电子态之间的相互作用，这是量子化学中许多其他高精度方法所面临的挑战。MC-PDFT被广泛应用于光化学、催化、超分子化学和光谱学系统，因此在先进制造、可再生能源和化学工业中具有相关性。除了该方法可能对计算化学社区产生的广泛影响外，该提案的更广泛影响是两位研究人员的专业知识的结合，这使学生能够从更广泛的思想中受益，从而有助于全面的职业准备。两位研究人员都鼓励女性进入科学事业，这有助于建立一个更多样化的科学队伍。Laura Gagliardi和Donald G. Truhlar正在开发多组态对密度泛函理论（MC-PDFT），这是一种将DFT与多组态波函数相结合的固有多组态系统的最新方法。他们的工作从三个方向扩展了这一理论。首先，他们正在开发计算状态平均计算的解析梯度的方法，这一特征对于探索激发态非常重要。其次，他们正在开发一种状态相互作用方法，用于处理锥形交叉口附近区域的多个电子态。第三，他们正在将MC-PDFT整合到其他软件中，并将该方法应用于过渡金属系统和激发态。这一提议的一个更广泛的影响是将两位研究者的专业知识结合起来，让学生从广泛的思想中受益，从而为全面的职业准备做出贡献。其他重要的更广泛的影响源于所选择的研究主题的技术重要性，特别是对健康，社会的物质需求，工业竞争力和国防。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

Laura Gagliardi and Donald G. Truhlar of the University of Minnesota are supported by an award from the Chemical Theory, Models and Computational Methods program in the Chemistry Division to develop a theory that enables high-accuracy calculations on chemical reactions on large systems. This method, Multi-Configuration Pair-Density Functional Theory (MC-PDFT), was recently introduced as a practical way to treat reactions where bonds are breaking, situations where electrons are excited, or systems that contain transition metals. All of these examples involve interactions among multiple electronic states, that are challenging problems for many other high accuracy methods in quantum chemistry. MC-PDFT is being broadly applied to systems in photochemistry, catalysis, supramolecular chemistry, and spectroscopy and thus has relevance in advanced manufacturing, renewable energy, and the chemical industry. In addition to the wide impact the method may have on the computational chemistry community, a broader impact of this proposal is the combination of expertise of two investigators, which allows students to benefit from a wider range of ideas and thereby contributes to well-rounded career preparation. Both investigators encourage women to enter scientific careers which contributes to a more diverse scientific workforce. Laura Gagliardi and Donald G. Truhlar are developing Multi-Configuration Pair-Density Functional Theory (MC-PDFT), a recent method for inherently multiconfigurational systems, that combines DFT with multiconfiguration wave functions. Their work is extending the theory in three directions. First, they are developing methods to calculate analytic gradients for state-averaged calculations, a feature that is important to enable exploration of excited states. Second, they are developing a state interaction method for treating multiple electronic states in regions near conical intersections. Third, they are incorporating MC-PDFT into additional software and are applying the methods to transition metal systems and excited states. One broader impact of this proposal is to combine the expertise of two investigators to allow students to benefit from a wide range of ideas, thereby contributing to well-rounded career preparation. Other important broader impacts stem from the technological importance of the research subjects chosen, especially for health, the material needs of society, industrial competitiveness, and defense.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.