Incremental evaluation of coupled cluster dipole polarizabilities

In this work we present the first implementation of the incremental scheme for coupled cluster linear-response frequency-dependent dipole polarizabilities. The implementation is fully automated and makes use of the domain-specific basis set approach. The accuracy of the approach is determined on the basis of a test suite of 47 molecules and small clusters. The local approximation in the coupled cluster singles and doubles polarizability exhibits a mean error of 0.02% and a standard deviation of 0.32% when using a third-order incremental expansion. With the proposed approach, it is possible to compute polarizabilities with larger basis sets compared to the canonical implementation and thus it is possible to obtain higher total accuracy. The incremental scheme yields the smallest errors for weakly-bound and quasi-linear systems, while two- and three-dimensional (cage-like) structures exhibit somewhat larger errors as compared to the full test set.Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich

Comparison of Small Molecule and Polymeric Urethanes, Thiourethanes, and Dithiourethanes: Hydrogen Bonding and Thermal, Physical, and Mechanical Properties

The hydrogen bonding behavior of a homologous series of small molecule and polymeric urethanes, thiourethanes. and dithiourethanes was investigated in solution, melt, and solid states. The relative hydrogen bonding strengths in both small molecule and polymer systems were evaluated, and the results were compared to theoretical calculations of hydrogen bonding strength. The results for NMR and FTIR analysis of the small molecule models indicated that the NH protons on the carbamate and thiocarbamates have greater hydrogen bonding strengths than the NH protons of the dithiocarbamate. The polyurethane and polythiourethanes were found to have approximately equivalent physical and mechanical properties as a result of a similar extent of hydrogen bonding, whereas the polydithiourethane, due to a lower degree of hydrogen bonding, has reduced thermal and mechanical transition temperatures as well as lower hardness values. The polythiourethane and polydithiourethane networks exhibit narrower glass transitions compared to polyurethane networks., apparently the result of an efficient isocyanate/isothiocyanate-thiol reaction with little or no side products. Because of weakness of the C-S bond compared to the C-O bond, thiourethanes and dithiourethanes have lower thermal stability than the corresponding urethanes. Finally, the polythiourethanes and polydithiourethane have higher refractive index values than their polyurethane Counterpart

Psi4 1.1: An Open-Source Electronic Structure Program Emphasizing Automation, Advanced Libraries, and Interoperability

Psi4 is an ab initio electronic structure program providing methods such as Hartree-Fock, density functional theory, configuration interaction, and coupled-cluster theory. The 1.1 release represents a major update meant to automate complex tasks, such as geometry optimization using complete-basis-set extrapolation or focal-point methods. Conversion of the top-level code to a Python module means that Psi4 can now be used in complex workflows alongside other Python tools. Several new features have been added with the aid of libraries providing easy access to techniques such as density fitting, Cholesky decomposition, and Laplace denominators. The build system has been completely rewritten to simplify interoperability with independent, reusable software components for quantum chemistry. Finally, a wide range of new theoretical methods and analyses have been added to the code base, including functional-group and open-shell symmetry adapted perturbation theory, density-fitted coupled cluster with frozen natural orbitals, orbital-optimized perturbation and coupled-cluster methods (e.g., OO-MP2 and OO-LCCD), density-fitted multiconfigurational self-consistent field, density cumulant functional theory, algebraic-diagrammatic construction excited states, improvements to the geometry optimizer, and the "X2C" approach to relativistic corrections, among many other improvements