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The direct random-phase approximation (dRPA) is used to calculate and compare atomization energies for the HEAT set and 10 selected molecules of the G2-1 set using both plane waves and Gaussian-type orbitals. We describe detailed procedures to obtain highly accurate and well converged results for the projector augmented-wave (PAW) method as implemented in the Vienna Ab-initio Simulation Package (VASP) as well as the explicitly correlated dRPA-F12 method as implemented in the TURBOMOLE package. The two approaches agree within chemical accuracy (1 kcal/mol) for the atomization energies of all considered molecules, both for the exact exchange as well as for the dRPA. The root mean-square deviation is 0.41 kcal/mol for the exact exchange (evaluated using density functional theory orbitals) and 0.33 kcal/mol for exact exchange plus the random-phase approximation., Comment: 16 pages, 2 figures

We establish a link between quantum mechanical molecular simulations and the transfer matrix of a molecule. The transfer matrix (T-matrix) of an object provides a complete description of its electromagnetic response. Once the T-matrices of the individual components of an ensemble are known, the electromagnetic response of the ensemble can be efficiently computed. This holds for arbitrary arrangements of large number of molecules, as well as for periodic arrays. We provide T-matrix based formulas for computing traditional chiro-optical properties like Circular Dichroism and Oriented Circular Dichroism, and also for quantifying electromagnetic duality and electromagnetic chirality, two properties that are fundamentally related to chiral interactions, and also technologically relevant. The formulas are valid for light-matter interactions of arbitrary high multipolar orders. We exemplify our approach by first computing the T-matrix of a cross-like arrangement of four copies of a chiral molecule from the time-dependent Hartree-Fock theory simulation data of the individual molecule, and then computing the aforementioned electromagnetic properties of both the cross and the individual molecule. The link that we establish is a necessary step towards obtaining T-matrix based constitutive relations of general bulk molecular materials from quantum mechanical simulations of their molecular constituents.

In a previous contribution (Mol. Phys. {\bf 103}, xxxx, 2005), we established the suitability of density functional theory (DFT) for the calculation of molecular anharmonic force fields. In the present work, we have assessed a wide variety of basis sets and exchange-correlation functionals for harmonic and fundamental frequencies, equilibrium and ground-state rotational constants, and thermodynamic functions beyond the RRHO (rigid rotor-harmonic oscillator) approximation. The fairly good performance of double-zeta plus polarization basis sets for frequencies results from an error compensation between basis set incompleteness and the intrinsic error of exchange-correlation functionals. Triple-zeta plus polarization basis sets are recommended, with an additional high-exponent $d$ function on second-row atoms. All conventional hybrid GGA functionals perform about equally well: high-exchange hybrid GGA and meta-GGA functionals designed for kinetics yield poor results, with the exception of of the very recently developed BMK functional which takes a middle position along with the HCTH/407 (second generation GGA) and TPSS (meta-GGA) functionals. MP2 performs similarly to these functionals but is inferior to hybrid GGAs such as B3LYP and B97-1., Comment: Int. J. Quantum Chem., in press (special issue on vibrational spectroscopies)

The very good performance of modern density functional theory for molecular geometries and harmonic vibrational frequencies has been well established. We investigate the performance of density functional theory (DFT) for quartic force fields, vibrational anharmonicity and rotation-vibration coupling constants, and thermodynamic functions beyond the RRHO (rigid rotor-harmonic oscillator) approximation of a number of small polyatomic molecules. Convergence in terms of basis set, integration grid and the numerical step size for determining the quartic force field by using central differences of analytical second derivatives has been investigated, as well as the performance of various exchange-correlation functionals. DFT is found to offer a cost-effective approach with manageable scalability for obtaining anharmonic molecular properties, and particularly as a source for anharmonic zero-point and thermal corrections for use in conjunction with benchmark {\it ab initio} thermochemistry methods., Comment: Molecular Physics, in press (N. C. Handy special issue)