Modern electronic structure approaches facilitate unprecedented predictions of molecular and materials properties in complex systems. However, quantum mechanics is at odds with the language of synthetic chemistry, as becomes evident e.g. when contrasting intrinsically indistinguishable electrons with the concept of distinguishable functional groups responsible for molecular reactivities and properties. As a result, basing the optimization of a specific molecular property on first principles prediction remains somewhat of a trial-and-error process that lacks immediate information about structure-property relations that could inform rational synthesis. To address this challenge, we: 1. developed a first principles approach to predict contributions of individual molecular subsystems to linear response properties such as polarizabilities, magnetizabilities, and spectroscopic constants, 2. developed a linear-scaling approach to expedite linear response predictions on complex systems, 3. applied these approaches to optimize nanoelectromechanical systems for ultralow-power electronics and nano-sensing, and 4. applied energy decomposition analysis to rationalize ultrafast vibrational spectroscopy experiments to yield a molecular understanding of carbon capture in ionic liquids. In summary, this work facilitates a comprehensive understanding of the molecular mechanisms underlying molecular response properties, it informs the construction of empirical models such structure-function relations from first principles, and helps guide rational synthesis of molecules to optimize a desired response property.

Constructing optimal structure-function relations directly from first principles

255th National Meeting (2018)

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