Molecular-orbital-free algorithm for the excited-state force in time-dependent density functional theory

Liu, Jie; Liang, Wan Zhen
January 2011
Journal of Chemical Physics;1/28/2011, Vol. 134 Issue 4, p044114
Academic Journal
Starting from the equation of motion in the density matrix formulation, we reformulate the analytical gradient of the excited-state energy at the time-dependent density functional theory level in the nonorthogonal Gaussian atom-centered orbital (AO) basis. Analogous to the analytical first derivative in molecular-orbital (MO) basis, a Z-vector equation has been derived with respect to the reduced one-electronic density matrix in AO basis, which provides a potential possibility to exploit quantum locality of the density matrix and avoids the matrix transformation between the AO and the MO basis. Numerical tests are finished for the excited-state geometry optimization and adiabatic excitation energy calculation of a series of small molecules. The results demonstrate the computational efficiency and accuracy of the current AO-based energy gradient expression in comparison with the MO-based scheme.


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