The complex linear polarization propagator approach has been applied to the calculation of electronic circular dichroism spectra of 3R-chloro-1-butyne, 3R-methylcyclopentanone, 3S-methylcyclohexanone, 4R-1,1-dimethyl-[3]-(1,2)ferrocenophan-2-on, S-3,3,3',3'-tetramethyl-1,1'-spirobi[3H,2,1]-benzoxaselenole, and the fullerene C84. Using time-dependent Kohn-Sham density functional theory, it is shown that a direct and efficient evaluation of the circular dichroism spectrum can be achieved. The approach allows for the determination of the circular dichroism at an arbitrary wavelength thereby, in a common formulation and implementation, covering the visible, ultraviolet, and x-ray regions of the spectrum. In contrast to traditional methods, the entire manifold of excited states is taken into account in the calculation of the circular dichroism at a given wavelength.

The frequency-dependent polarizabilities and the C6 dipole-dipole dispersion coefficients for the first members of the polyacenes namely benzene, naphthalene, anthracene, and naphthacene as well as the fullerene C60 have been calculated at the time-dependent Hartree-Fock level and the time-dependent density-functional theory level with the hybrid B3LYP exchange-correlation functional. The dynamic polarizabilities at imaginary frequencies are obtained with use of the complex linear polarization propagator method and the C6 coefficients are subsequently determined from the Casimir-Polder relation. We report the first ab initio calculations of the C6 coefficients for the molecules under consideration, and our recommended value for the dispersion coefficient of the fullerene is 101.0 a.u.

The complex polarization propagator method [J. Chem. Phys. 123, 194103 (2005)] has been employed in conjunction with density functional theory and gauge-including atomic orbitals in order to determine the near-edge x-ray absorption and natural circular dichroism spectra of L-alanine in its neutral and zwitterionic forms. Results are presented for the K-edges of carbon, nitrogen, and oxygen. In contrast to traditional methods, the proposed approach enables a direct determination of the spectra at an arbitrary frequency instead of focusing on the rotatory strengths for individual electronic transitions. The propagator includes a complete set of nonredundant electron-transfer operators and allows for full core-hole relaxation. The theoretical spectrum at the nitrogen K-edge of the zwitterion compares well with the experimental spectrum.

The frequency-dependent polarizabilities of closed-shell sodium clusters containing up to 20 atoms have been calculated using the linear complex polarization propagator approach in conjunction with Hartree-Fock and Kohn-Sham density functional theories. In combination with polarizabilities for C 60 from a previous work ͓J. Chem. Phys. 123, 124312 ͑2005͔͒, the C 6 dipole-dipole dispersion coefficients for the metal-cluster-to-cluster and cluster-to-buckminster-fullerene interactions are obtained via the Casimir-Polder relation ͓Phys. Rev. 73, 360 ͑1948͔͒. The B3PW91 results for the polarizability of the sodium dimer and tetramer are benchmarked against coupled cluster calculations. The error bars of the reported theoretical results for the C 6 coefficients are estimated to be 5%, and the results are well within the error bars of the experiment.

The linear polarization propagator has been computed at imaginary frequencies for He, Ne, Ar, and Kr as well as for the n-alkanes including heptane and its smaller members. It is shown that an effective and direct evaluation of the polarization propagator using standard electronic structure first principle methods can be achieved on the whole imaginary axis without expanding the polarizability in a series of the Cauchy moments. The linear response equation will be complex in this case, but an effective algorithm can be constructed so that the computational cost parallels that of the real propagator. Calculations of the polarizability tensor are used to determine the Casimir–Polder interaction potentials for the molecules under consideration. Theoretical results for the C6 dispersion coefficient are compared with accurate experimental data, and it is shown that results for the extended n-alkanes obtained with density functional theory and the hybrid B3LYP exchange correlation functional are in excellent agreement with experiment. At the same level of theory, on the other hand, there are significant discrepancies for the noble gas atoms. The electron correlation contribution to C6 is less than 9% for the n-alkanes and decreases with the size of the system.