A multiconfiguration time‐dependent Hartree approximation based on natural single‐particle states

The time‐dependent Schrodinger equation is solved with a multiconfiguration form for the state. It is shown that the use of natural single‐particle states results in a minimal number of configurations. The equations of motion of the natural single‐particle states are derived by differentation with respect to time of the defining equations, which are eigenvalue equations of reduced density matrices. The method is tested on a two‐dimensional model of H2 dissociation on a transition metal surface. It is shown that numerically exact solutions can be obtained. Computation times and memory requirements are less than for methods that solve the time‐dependent Schrodinger equation directly.

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