Potential energy surface electronic structure, global surfaces

A. Electronic Structure Global Potential Energy Surfaces... 

In addition to the carbenium-carbonium dications (i.e. 35), bis-carbonium dications have been studied by theoretical methods. Examination of the potential energy surface of C3Hio2+ (diprotonated propane) finds three structures at energy minima.18 The global minimum corresponds to the structure (37) in which both terminal carbons are involved in electron-deficient 2e-3c bonds. The next most stable C3Hio2+ structure (38) lies 6.7 kcal/mol higher in energy and it possesses two 2e-3c bonds,... 

The most basic information that is needed for constructing a global potential energy surface for gas phase MD simulations is the structures and vibrational frequencies. The earliest information about gas-phase RDX molecular structures was obtained from theoretical calculations [54-58]. In 1984 Karpowicz and Brill [59] reported Fourier transform infrared spectra for vapor-phase (and for the a - and p -phase) RDX in 1984, however, their data precluded a complete description of the molecular conformations and vibrational spectroscopy. More recently, Shishkov et al. [60] presented a more complete description based on electron-scattering data and molecular modeling. They concluded that the data were best reproduced by RDX in the chair conformation with all the nitro groups in axial positions. 

The difference from classical force field based simulations where the forces are calculated from pre-defined pair potentials is that the forces are derived from the global potential energy surface of an electronic structure theory. The vastly higher computational costs of an electronic structure calculation restrict the system size and the length of trajectories accessible by ab initio molecular dynamics simulations. However, it becomes clear that CPMD and AIMD are important steps towards general predictive methods, due to their independence from parameterizations. 

Early LSDA static pseudopotential approaches to sodium microclusters date back approximately 20 years [122], see Appendix C. It would be misleading to consider LDA calculations as the natural extension of jellium models. However, the global validity of the latter cannot but anticipate the success of the former. Clearly, these should also clarify the role of the atomic structure in determining the electronic behavior of the clusters and the extent to which the inhomogeneity of the electron distribution is reflected in the measurable properties. Many structural determinations are by now available for the smaller aggregates, made at different levels of approximation and of accuracy (e.g. [110, 111], see Appendix C). The most extensive investigation of sodium clusters so far is the LDA-CP study of Ref. [123] (see Appendix C), which makes use of all the features of the CP method. Namely, it uses dynamical SA to explore the potential-energy surface, MD to simulate clusters at different temperatures, and detailed analysis of the one-electron properties, which can be compared to the predictions of jellium-based models. 

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