Multipolar analysis of the hyperpolarizability tensor, as commonly measured by hyper-Rayleigh scatting (HRS) experiments, provides insight as to the local multipolar structure of elementary scatterers, such as liquid-clusters and interfaces. The fragment molecular orbital (FMO) and linear response time-dependent density functional theory (LR-TDDFT) methods have been combined to facilitate the ab inito calculation of 2nd and 3rd order optical properties for large systems, including the hyperpolarizability and HRS depolarization ratio. The linearly scaling FMO/LR-TDDFT method for the calculation of nonlinear optical properties on large systems is described, as is its preliminary application in studying the local structure of room-temperature ionic liquids (RTIL), with the goal of matching structures sampled from molecular dynamics simulations with HRS experiment.

Nonlinear optical structural properties of room-temperature ionic liquids, calculated with the combined fragment molecular orbital and linear-response time-dependent density functional theory method (FMO/LR-TDDFT)

249th National Meeting (2015)

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