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At any resolution level of wavelet expansions the physical observable of the kinetic energy is represented by an infinite matrix which is ``canonically chosen as the projection of the operator $-Delta/2$ onto the subspace of the given resolution. It is shown, that this canonical choice is not optimal, as the regular grid of the basis set introduces an artificial consequence of periodicity, and it is only a particular member of possible operator representations. We present an explicit method of preparing a near optimal kinetic energy matrix which leads to more appropriate results in numerical wavelet based calculations. This construction works even in those cases, where the usual definition is unusable (i.e., the derivative of the basis functions does not exist). It is also shown, that building an effective kinetic energy matrix is equivalent to the renormalization of the kinetic energy by a momentum dependent effective mass compensating for artificial periodicity effects.
A semiempirical parametric method is proposed for modeling three-dimensional (time-resolved) vibronic spectra of polyatomic molecules. The method is based on the use of the fragment approach in the formation of molecular models for excited electronic
A concept of Kinetic Energy in Quantum Mechanics is analyzed. Kinetic Energy is not zero in many cases where there are no motion and flux. This paradox can be understood, using expansion of the wave function in Fourier integral, that is on the basis of virtual plane waves.
Linear-response time-dependent (TD) density-functional theory (DFT) has been implemented in the pseudopotential wavelet-based electronic structure program BigDFT and results are compared against those obtained with the all-electron Gaussian-type orbi
We construct the complementary short-range correlation relativistic local-density-approximation functional to be used in relativistic range-separated density-functional theory based on a Dirac-Coulomb Hamiltonian in the no-pair approximation. For thi
We develop relativistic short-range exchange energy functionals for four-component relativistic range-separated density-functional theory using a Dirac-Coulomb Hamiltonian in the no-pair approximation. We show how to improve the short-range local-den