An effective formalism for quantum constrained systems is presented which allows manageable derivations of solutions and observables, including a treatment of physical reality conditions without requiring full knowledge of the physical inner product. Instead of a state equation from a constraint operator, an infinite system of constraint functions on the quantum phase space of expectation values and moments of states is used. The examples of linear constraints as well as the free non-relativistic particle in parameterized form illustrate how standard problems of constrained systems can be dealt with in this framework.

We apply the formalism of quantum cosmology to models containing a phantom field. Three models are discussed explicitly: a toy model, a model with an exponential phantom potential, and a model with phantom field accompanied by a negative cosmological constant. In all these cases we calculate the classical trajectories in configuration space and give solutions to the Wheeler-DeWitt equation in quantum cosmology. In the cases of the toy model and the model with exponential potential we are able to solve the Wheeler-DeWitt equation exactly. For comparison, we also give the corresponding solutions for an ordinary scalar field. We discuss in particular the behaviour of wave packets in minisuperspace. For the phantom field these packets disperse in the region that corresponds to the Big Rip singularity. This thus constitutes a genuine quantum region at large scales, described by a regular solution of the Wheeler-DeWitt equation. For the ordinary scalar field, the Big-Bang singularity is avoided. Some remarks on the arrow of time in phantom models as well as on the relation of phantom models to loop quantum cosmology are given.Comment: 21 pages, 6 figure

We investigate a cosmological model with a big-brake singularity in the future: while the first time derivative of the scale factor goes to zero, its second time derivative tends to minus infinity. Although we also discuss the classical version of the model in some detail, our main interest lies in its quantization. We formulate the Wheeler-DeWitt equation and derive solutions describing wave packets. We show that all such solutions vanish in the region of the classical singularity, a behaviour which we interpret as singularity avoidance. We then discuss the same situation in loop quantum cosmology. While this leads to a different factor ordering, the singularity is there avoided, too.

Classical models for dark energy can exhibit a variety of singularities, many of which occur for scale factors much bigger than the Planck length. We address here the issue whether some of these singularities, the big freeze and the big démarrage, can be avoided in quantum cosmology. We use the framework of quantum geometrodynamics. We restrict our attention to a class of models whose matter content can be described by a generalized Chaplygin gas and be represented by a scalar field with an appropriate potential. Employing the DeWitt criterium that the wave function be zero at the classical singularity, we show that a class of solutions to the Wheeler-DeWitt equation fulfilling this condition can be found. These solutions thus avoid the classical singularity. We discuss the reasons for the remaining ambiguity in fixing the solution.

We report on applications of the domain based local pair-natural orbital (PNO) coupled-cluster method within the singles and doubles approximation (DLPNO-CCSD) to the calculation of 57Fe isomer shifts and quadrupole splittings in a small training set of iron complexes consisting of large molecular ligands and iron atoms in varying charge, spin, and oxidation states. The electron densities and electric field gradients needed for these calculations were obtained within the recently implemented analytic derivative scheme. A method for the direct treatment of scalar relativistic effects in the calculation of effective electron densities is described by using the first-order Douglas–Kroll–Hess Hamiltonian and a Gaussian charge distribution model for the nucleus. The performance of DLPNO-CCSD is compared with four modern-day density functionals, namely, RPBE, TPSS, B3LYP, and B2PLYP, as well as with the second-order Møller–Plesset perturbation theory. An excellent correlation between the calculated electron densities and the experimental isomer shifts is attained with the DLPNO-CCSD method. The correlation constant a obtained from the slope of the linear correlation plot is found to be ≈−0.31 a.u.3 mm s−1, which agrees very well with the experimental calibration constant α = −0.31 ± 0.04 a.u.3 mm s−1. This value of a is obtained consistently using both nonrelativistic and scalar relativistic DLPNO-CCSD electron densities. While the B3LYP and B2PLYP functionals achieve equally good correlation between theory and experiment, the correlation constant a is found to deviate from the experimental value. Similar trends are observed also for quadrupole splittings. The value of the nuclear quadrupole moment for 57Fe is estimated to be 0.15 b at the DLPNO-CCSD level. This is consistent with previous results and is here supported by a higher level of theory. The DLPNO-CCSD results are found to be insensitive to the intrinsic approximations in the method, in particular the PNO occupation number truncation error, while the results obtained with density functional theory (DFT) are found to depend on the choice of the functional. In a statistical sense, i.e., on the basis of the linear regression analysis, however, the accuracies of the DFT and DLPNO-CCSD results can be considered comparable.