Ab initio calculations with a nonspherical Gaussian basis set: Excited states of the hydrogen molecule

A basis set of generalized nonspherical Gaussian functions (GGTOs) is presented and discussed. As a first example we report on Born-Oppenheimer energies of the hydrogen molecule. Although accurate results have been obtained, we conclude that H_2 is too 'simple' to allow for a substantial gain by using nonspherical functions. We rather expect that these functions may be particularly useful in calculations on large systems. A single basis set of GGTOs was used to simultaneously calculate the potential energy curves of several states within each subspace of {1,3}\Sigma_{g,u} symmetry. We hereby considerd the entire region of internuclear distances 0.8 < R < 1000 a.u. In particular the results for the fourth up to sixth electronic states show a high accuracy compared to calculations which invoke explicitely correlated functions, e.g. the relative accuracy is at least of the order of magnitude of 10^{-5}a.u. Energies for the 4 ^1\Sigma_u^+ and 4-6 ^3\Sigma_u^+ were improved and accurate data for the 6 ^3\Sigma_g^+, 5 ^1\Sigma_u^+, and 6 ^1\Sigma_u^+ state are, to the best of the authors knowledge, presented for the first time. Energy data for the seventh up to the nineth electronic state within each subspace were obtained with an estimated error of the order of magnitude of 10^{-4}a.u. The 7 ^1\Sigma_g^+ and the 6 ^1\Sigma_u^+ state were found to exhibit a very broad deep outer well at large internuclear distances.Comment: 4 figures, subm.to J.Chem.Phy

On the Cholesky Decomposition for electron propagator methods: General aspects and application on C60

To treat the electronic structure of large molecules by electron propagator methods we developed a parallel computer program called P-RICD$\Sigma$. The program exploits the sparsity of the two-electron integral matrix by using Cholesky decomposition techniques. The advantage of these techniques is that the error introduced is controlled only by one parameter which can be chosen as small as needed. We verify the tolerance of electron propagator methods to the Cholesky decomposition threshold and demonstrate the power of the P-RICD$\Sigma$ program for a representative example (C60). All decomposition schemes addressed in the literature are investigated. Even with moderate thresholds the maximal error encountered in the calculated electron affinities and ionization potentials amount to a few meV only, and the error becomes negligible for small thresholds.Comment: 30 pages, 6 figures submitted to J.Chem. Phy

Pathway from condensation via fragmentation to fermionization of cold bosonic systems

For small scattering lengths, cold bosonic atoms form a condensate the density profile of which is smooth. With increasing scattering length, the density {\it gradually} acquires more and more oscillations. Finally, the number of oscillations equals the number of bosons and the system becomes {\it fermionized}. On this pathway from condensation to fermionization intriguing phenomena occur, depending on the shape of the trap. These include macroscopic fragmentation and {\it coexistence} of condensed and fermionized parts that are separated in space.Comment: 12 pages, 2 figure

Interferences in the density of two Bose-Einstein condensates consisting of identical or different atoms

The density of two {\it initially independent} condensates which are allowed to expand and overlap can show interferences as a function of time due to interparticle interaction. Two situations are separately discussed and compared: (1) all atoms are identical and (2) each condensate consists of a different kind of atoms. Illustrative examples are presented.Comment: 12 pages, 3 figure

On interacting fermions and bosons with definite total momentum

Any {\it exact} eigenstate with a definite momentum of a many-body Hamiltonian can be written as an integral over a {\it symmetry-broken} function $\Phi$. For two particles, we solve the problem {\it exactly} for all energy levels and any inter-particle interaction. Especially for the ground-state, $\Phi$ is given by the simple Hartree-Fock/Hartree ansatz for fermions/bosons. Implications for several and many particles as well as a numerical example are provided