Accuracy nuclear properties with

Uncertainties of the conventional parameters of H-atoms have been addressed since the early applications of X-ray charge density method. Support from ND measurements appears to be essential, because the neutron scattering power is a nuclear property (it is independent of the electronic structure and the scattering angle). The accuracy of nuclear parameters obtained from ND data thus depends mainly on the extent to which dynamic effects (most markedly thermal diffuse scattering) and extinction are correctable. Problems associated with different experimental conditions and different systematic errors affecting the ND and XRD measurements have to be addressed whenever a joint interpretation of these data is attempted. This has become apparent in studies which aimed either to refine XRD and ND data simultaneously [59] (commonly referred to as the X+N method), or to impose ND-derived parameters directly into the fit of XRD data (X—N method) [16]. In order to avoid these problems, usually only the ND parameters of the H-atoms are used and fixed in the XRD refinement (X-(X+N) method). 

Concerning the nuclear properties it may be noted that the ratio of the nuclear quadrupole moments of the isotopes of chlorine and bromine have been determined with considerably higher accuracy than have the individual quadrupole moments. NMR spectroscopy has been frequently applied to determine nuclear magnetic moments and all the nuclear magnetic properties listed in Table 1.1 were obtained from... 

Molecular dynamic studies used in the interpretation of experiments, such as collision processes, require reliable potential energy surfaces (PES) of polyatomic molecules. Ab initio calculations are often not able to provide such PES, at least not for the whole range of nuclear configurations. On the other hand, these surfaces can be constructed to sufficiently good accuracy with semi-empirical models built from carefully chosen diatomic quantities. The electric dipole polarizability tensor is one of the crucial parameters for the construction of such potential energy curves (PEC) or surfaces [23-25]. The dependence of static dipole properties on the internuclear distance in diatomic molecules can be predicted from semi-empirical models [25,26]. However, the results of ab initio calculations for selected values of the internuclear distance are still needed in order to test and justify the reliability of the models. Actually, this work was initiated by F. Pirani, who pointed out the need for ab initio curves of the static dipole polarizability of diatomic molecules for a wide range of internuclear distances. 

Nonrelativistic quantum mechanics, extended by the theory of electron spin and by the Pauli exclusion principle, provides a reliable theory for the computation of atomic spectral frequencies and intensities, of cross sections for scattering or capture of electrons by atomic systems, of chemical bonds and many properties of solids, including magnetic properties, although with much more complicated systems it has not always proved possible to develop with adequate accuracy the consequences of the theory. Quantum mechanics has also had a limited success in nuclear theory although m this field it is possible that a more fundamental system of mechanics is required. 

In theory, a properly developed force field should be able to reproduce structures, strain energies, and vibrations with similar accuracies since the three properties are interrelated. However, structures are dependent on the nuclear coordinates (position of the energy minima), relative strain energies depend on the steepness of the overall potential (first derivative), and nuclear vibrations are related to the curvature of the potential energy surface (second derivative). Thus, force fields used successfully for structural predictions might not be satisfactory for conformational analyses or prediction of vibrational spectra, and vice versa. The only way to overcome this problem is to include the appropriate type of data in the parameterization process 501. 

In the case of the positronium spectrum the accuracy is on the MHz-level for most of the studied transitions (Is hyperfine splitting, Is — 2s interval, fine structure) [13] and the theory is slightly better than the experiment. The decay of positronium occurs as a result of the annihilation of the electron and the positron and its rate strongly depends on the properties of positronium as an atomic system and it also provides us with precise tests of bound state QED. Since the nuclear mass (of positronium) is the positron mass and me+ = me-, such tests with the positronium spectrum and decay rates allow one to check a specific sector of bound state QED which is not available with any other atomic systems. A few years ago the theoretical uncertainties were high with respect to the experimental ones, but after attempts of several groups [17,18,19,20] the theory became more accurate than the experiment. It seems that the challenge has been undertaken on the experimental side [13]. 

H. We understood H to be complete and including electronic as well as nuclear degrees of freedom, and in which case the states are the true nonadiabatlc vlbronic eigenstates of the system and hence the properties are the exact ones. Nothing prevents us, however, to introduce the adiabatic approximation and to assume the wave functions to be products of electronic and nuclear (vibrational) parts. In this case, the Born-Oppenheimer electronic plus vibrational properties will appear. We can even reduce the accuracy to the extent that we adopt the electronic Hamiltonian, work with the spectrum of electronic states, and thus extract the electronic part of the properties. In all these cases, the SOS property expressions remain unchanged. 

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