Properties of atoms in electronically excited molecules within the formalism of TDDFT.

The topological analysis of the electron density for electronic excited states under the formalism of the quantum theory of atoms in molecules using time-dependent density functional theory (TDDFT) is presented. Relaxed electron densities for electronic excited states are computed by solving a Z-vector equation which is obtained by means of the Sternheimer interchange method. This is in contrast to previous work in which the electron density for excited states is obtained using DFT instead of TDDFT, that is, through the imposition of molecular occupancies in accordance with the electron configuration of the excited state under consideration.

Subshell fitting of relativistic atomic core electron densities for use in QTAIM analyses of ECP-based wave functions.

Scalar-relativistic, all-electron density functional theory (DFT) calculations were done for free, neutral atoms of all elements of the periodic table using the universal Gaussian basis set. Each core, closed-subshell contribution to a total atomic electron density distribution was separately fitted to a spherical electron density function: a linear combination of s-type Gaussian functions. The resulting core subshell electron densities are useful for systematically and compactly approximating total core electron densities of atoms in molecules, for any atomic core defined in terms of closed subshells.

Atomic partitioning of the dissociation energy of the P-O(H) bond in hydrogen phosphate anion (HPO4(2-)): disentangling the effect of Mg2+.

This paper has three goals: (1) to provide a first step in understanding the atomic basis of the role of magnesium in facilitating the dissociation of the P-O bond in phosphorylated biochemical fuel molecules (such as ATP or GTP), (2) to compare second-order Møller-Plesset perturbation theory (MP2) results with those obtained at the more economical density functional theory (DFT) level for a future study of larger more realistic models of ATP/GTP, and (3) to examine the calculation of atomic total energies from atomic kinetic energies within a Kohn-Sham implemention of DFT, as compared to ab initio methods. A newly described method based on the quantum theory of atoms in molecules (QTAIM), which is termed the "atomic partitioning of the bond dissociation energy" (APBDE), is applied to a simple model of phosphorylated biological molecules (HPO42-). The APBDE approach is applied in the presence and in the absence of magnesium.

NMR chemical shifts. Substituted acetylenes.

The MPW1PW91/6-311+G(2d,p) and MP2/6-311+G(2d,p) GIAO nuclear shieldings for a series of monosubstituted acetylenes have been calculated using the MP2/6-311G(2d,p) geometries. Axially symmetric substituents such as fluorine may lead to large changes in the isotropic shielding but have little effect on the tensor component (zz) about the C[triple bond]C bond axis. On the other hand, substituents such as vinyl and aldehyde groups lead to essentially no difference in the isotropic shielding but are calculated to give a large zz paramagnetic shift to the terminal carbon of the acetylene group, without having much effect on the inner carbon.