Transition energies, calculation system

This functional gives accurate results for all the systems shown in the table. Thus, the MLSDSIC functional can be employed for calculating the transition energies of electronic systems. In Section 5.6, we present the results for transition energies calculated by employing this functional. 

Representative applications of the NVPA Fock-space CC method to actinide systems are presented below. Many calculations have been carried out over the last 15 years, involving various heavy and superheavy atomic and molecular systems (not limited to actinides), with dozens of transition energies calculated per system. Most atomic results agreed with experiment within a few hundredths of an eV. Molecular applications of the RFSCC are less precise, due to the symmetry limitations on molecular basis sets. Still, our calculations of heavy molecular systems, including actinide compounds, yield state-of-art benchmark molecular parameters. A fuller description may be found in the original publications and in our recent reviews [6,7]. 

The active space used for both systems in these calculations is sufficiently large to incorporate important core-core, core-valence, and valence-valence electron correlation, and hence should be capable of providing a reliable estimate of Wj- In addition to the P,T-odd interaction constant Wd, we also compute ground to excited state transition energies, the ionization potential, dipole moment (pe), ground state equilibrium bond length and vibrational frequency (ov) for the YbF and pe for the BaF molecule. 

Transition path sampling can also be helpful in the calculation of free energies in the context of fast-switching methods described in Chap. 5. As shown by Jarzynski [12], equilibrium free energies can be computed from the work performed on a system in repeated transformations carried out arbitrarily far from equilibrium. From a computational point of view, this remarkable theorem is attractive because it promises efficient free energy calculations due to the reduced cost of... 

Co2(CO)q system, reveals that the reactions proceed through mononuclear transition states and intermediates, many of which have established precedents. The major pathway requires neither radical intermediates nor free formaldehyde. The observed rate laws, product distributions, kinetic isotope effects, solvent effects, and thermochemical parameters are accounted for by the proposed mechanistic scheme. Significant support of the proposed scheme at every crucial step is provided by a new type of semi-empirical molecular-orbital calculation which is parameterized via known bond-dissociation energies. The results may serve as a starting point for more detailed calculations. Generalization to other transition-metal catalyzed systems is not yet possible. 

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