Density functionals covalent interactions

The observation that bonds of all orders relate to the bonding diagram in equivalent fashion indicates that covalent bonds are conditioned by the geometry of space, rather than the geometry of electron fields, dictated by atomic orbitals or other density functions. The only special point related to electron density occurs at the junction of the attractive curves, where e = indicating that one pair of electrons mediate the covalent interaction. It is interpreted as the limiting length (dj) for first-order bonds. It is of interest to note that all known first-order bonds have d > d[. The covalence curve for the minimum ratio of x = 0.18 (for CsH) terminates at dl = d[. 

Covalent interaction in diatomic molecules depends on the golden mean t, the interatomic distance d and the radius ratio x r /r2 of the constituent atoms, as summarized in Figure 5.6. The golden mean is a universal constant that matches the geometry and topology of space-time, the radius ratio is a known function of atomic number and dl relates to the optimal wave-mechanical distribution of valence-electron density in the diatomic system. 

Density functional theory (DFT) calculations of two types of push-pull chromophores built around thiophene-based 7t-conjugating spacers rigidified by either covalent bonds or noncovalent intramolecular interactions (Figure 6) have been carried out to assign the relevant electronic and vibrational features and to derive useful information about the molecular structure of these NLO-phores <2003CEJ3670>. 

Another approach to treating the boundary between covalently bonded QM and MM systems is the connection atom method,119 120 in which rather than a link atom, a monovalent pseudoatom is used. This connection atom is parameterized to give the correct behavior of the partitioned covalent bond. The connection atoms interact with the other QM atoms as a (specifically parameterized) QM atom, and with the other MM atoms as a standard carbon atom. This avoids the problem of a supplementary atom in the system, as the connection atom and the classical frontier atom are unified. However, the need to reparameterize for each type of covalent bond at a given level of quantum chemical theory is a laborious task.121 The connection atom method has been implemented for semiempirical molecular orbital (AMI and PM3)119 and density functional theory120 levels of theory. Tests carried out by Antes and Thiel to validate the connection atom method at the semiempirical level suggested that the connection atom approach is more accurate than the standard link atom approach.119... 

Twenty years ago Car and Parrinello introduced an efficient method to perform Molecular Dynamics simulation for classical nuclei with forces computed on the fly by a Density Functional Theory (DFT) based electronic calculation [1], Because the method allowed study of the statistical mechanics of classical nuclei with many-body electronic interactions, it opened the way for the use of simulation methods for realistic systems with an accuracy well beyond the limits of available effective force fields. In the last twenty years, the number of applications of the Car-Parrinello ab-initio molecular d3mam-ics has ranged from simple covalent bonded solids, to high pressure physics, material science and biological systems. There have also been extensions of the original algorithm to simulate systems at constant temperature and constant pressure [2], finite temperature effects for the electrons [3], and quantum nuclei [4]. 

While it is possible to account for non-covalent interactions using specialized force fields, common density functionals do not correctly describe the long-range van der Waals (London dispersion) interactions. Efficient dispersion correction schemes for DFT have been developed [14-17], but so far their application in QM/MM refinements is scarce. The importance of London forces for biomolecu-lar structures has been established conclusively [18]. 

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