Despite significant progress in functional development in recent years, serious problems remain for certain classes of applications of TDDFT. Well-known are the difficulties in obtaining long-range charge-transfer excitations non-empirically, and states of double excitation character, but modelling dynamics in real-time faces issues, some of which are, questionably, insurmountable. These include lack of memory-dependence, lack of accurate observable functionals, and the inability to change occupation numbers. For example, the fascinating problem of electronic quantum control at the attosecond scale, is hindered by the single-Slater determinant description. Time-dependent density-matrix functional theory has been recently explored as an alternative approach in which in principle, these difficulties are lessened. However, so far, adequate functional approximations have remained out of reach.  Here we review the challenges, and recent fixes, and then present a new approach, based on evaluating electron correlation via semiclassical dynamics. Calculations on simple systems show that this approach is a promising one; at the same time, they highlight potential limits to its applications.

Challenges in time-dependent DFT and DMFT: Can semiclassical correlation help?

242nd National Meeting (2011)

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