Extending the Usefulness of Time-Dependent Density Functional Theory: Dynamics, Excitations, and Coupling to Ions

PI将开发新的方法来解决当今时变密度泛函方法中几个最具挑战性的问题。项目涉及三个领域：强场中的电子动力学、激发和耦合电子-离子动力学。一个新的半经典方法的电子相关动力学将发展和应用于强场过程，特别是电子量子控制和电离。在这个领域，传统的波函数方法计算成本太高，而密度函数近似又缺乏内存，需要额外的可观察函数，并且无法改变占用数。所提出的方法解决了所有这些问题。新的非经验泛函将推导和测试，以研究远程电荷转移激发和双激发，这是传统密度泛函近似无法捕获的，从而导致全局精确的势能面。从第一性原理出发，将推导、分析和测试涉及核耦合到电子的半经典传播的方法，以处理相关的电子核动力学。这项工作将影响化学物理、原子和分子物理、生物分子和材料物理等领域的广泛现象。这项研究将促进我们对电子相互作用、动力学和激发在化学物理、原子和分子物理、材料科学（包括太阳能电池研究）等各个领域所起作用的基本理解。在这些领域将开发新的计算工具。该研究将密度泛函方法和半经典方法结合在一起，密度泛函方法是当今涉及许多电子的计算的主力，半经典方法通常用于简化和解释量子动力学。时变密度泛函理论的这些进展将克服早期在精确的全局分子动力学和光谱学计算中使用它的障碍。学生将接触到前沿的化学和物理基础理论研究。亨特大学现有的少数族裔服务项目将被用来促进未被充分代表的少数族裔科学家的发展。指导，无论是在小组内还是通过物理俱乐部的活动，将有助于指导和项目博士后，研究生和本科生走向科学导向的未来。他们将接触到PI在本科教学中使用的创新教学方法。

The PI will develop new approaches to several of the most challenging problems in time-dependent density functional methods today. The projects involve three areas: electron dynamics in strong fields, excitations, and coupled electron-ion dynamics. A novel semiclassical approach to electron correlation in dynamics will be developed and applied to strong-field processes, specifically electronic quantum control and ionization. This is an area in which traditional wavefunction methods are too computationally expensive yet density-functional approximations suffer from lack of memory, need for additional observable functionals, and the inability to change occupation numbers. The proposed method addresses all of these problems. New non-empirical functionals will be derived and tested to study long-range charge-transfer excitations and double-excitations, which conventional density functional approximations fail to capture, leading to globally accurate potential energy surfaces. Methods involving semiclassical propagation of nuclei coupled to electrons, starting from first-principles, will be derived, analyzed and tested, to treat correlated electron nuclear dynamics. This work will impact wide-ranging phenomena in chemical physics, atomic and molecular physics, biomolecules, and materials physics.The research will advance our fundamental understanding of the roles played by electron interactions, dynamics and excitations in a variety of areas such as chemical physics, atomic and molecular physics, and materials science, including solar cell research. New tools for computations in these fields will be developed. The research brings together density functional methods, today's workhorse for computations involving many electrons, and semiclassical methods, usually used to simplify and interpret quantum dynamics. These advances to time-dependent density functional theory will overcome earlier barriers to its use in calculation of accurate global molecular dynamics and spectroscopy. The students will be exposed to cutting-edge fundamental theoretical research in chemistry and physics. The existing minority-serving programs at Hunter will be leveraged to promote the development of underrepresented minority scientists. Mentoring, both within the group and via a Physics Club activity, will help guide and project postdoctoral fellows, graduate students and undergraduate students towards scientifically-oriented futures. They will be exposed to innovative teaching methods the PI uses for undergraduate teaching.