Correlated, Static and Dynamic Polarizabilities of Small Molecules. Comparison of Four “Black Box” Methods

Abstract

Molecular static and dynamic polarizabilities for thirteen small molecules have been calculated using four “black box” ab initio methods, the random phase approximation, RPA, the second-order polarization propagator approximation, SOPPA, the second-order polarization propagator approximation with coupled cluster singles and doubles amplitudes, SOPPA(CCSD), and the coupled cluster singles and doubles linear response function method, CCSDLR. The frequency dependence of the polarizabilities is given in terms of the dipole oscillator strength sum rules or Cauchy moments S(-4) and S(-6). Two basis sets were employed, Sadlej’s medium size polarized basis set and Dunning’s correlation consistent basis set of triple- œ quality augmented by two diffuse functions of each angular momentum (daug-cc-pVTZ). The results are compared to other theoretical results as well as to experimental values for the static polarizabilities, polarizability anisotropies, and Cauchy moments. Frequency-dependent polarizabilities and polarizability anisotropies, calculated at the CCSDLR level using the daug-cc-pVTZ basis set, are presented for five typical laser frequencies. The molecular dipole polarizability enters into the description of many physical and chemical processes, such as the scattering of light by molecules, and intermolecular interactions. Calculated polarizabilities are often used in the verification of experimental data and in the prediction of properties of new chemical species. An accuracy of a few percent in the calculated values is necessary for this purpose. Over the years several methods for the calculation of molecular properties have emerged. Among these are correlated methods, i.e. methods trying to improve on the Hartree-Fock approximation by perturbation theory or a multiconfigurational ansatz, as well as density functional theory (DFT) methods. Most of these methods, however, are only capable of calculating static properties like the static molecular polarizability, excitation energies, and transition moments. A direct comparison of calculated and experimental polarizabilities requires the ability to calculate frequency-dependent polarizabilities since experiments are mostly performed at nonzero frequencies. In an earlier study 1 the performance of some perturbation theory methods in the calculation of static polarizabilities was investigated. In this work, calculations of static and dynamic molecular polarizabilities are presented using four different “black box” methods, that is, methods where the only choices to be made are of the basis set and molecular geometry. These methods are in contrast to multiconfigurational methods where the selection of configurations to be included in the wave function requires considerable experience and might even become impossible for larger molecules. The black box methods, on the other hand, are relatively easy to use also by nonexperts, and their application is, apart from hardware limitations, not restricted to small molecules.