Rational bias

In this paper a method [11], which allows for an a priori BSSE removal at the SCF level, is for the first time applied to interaction densities studies. This computational protocol which has been called SCF-MI (Self-Consistent Field for Molecular Interactions) to highlight its relationship to the standard Roothaan equations and its special usefulness in the evaluation of molecular interactions, has recently been successfully used [11-13] for evaluating Eint in a number of intermolecular complexes. Comparison of standard SCF interaction densities with those obtained from the SCF-MI approach should shed light on the effects of BSSE removal. Such effects may then be compared with those deriving from the introduction of Coulomb correlation corrections. To this aim, we adopt a variational perturbative valence bond (VB) approach that uses orbitals derived from the SCF-MI step and thus maintains a BSSE-free picture. Finally, no bias should be introduced in our study by the particular approach chosen to analyze the observed charge density rearrangements. Therefore, not a model but a theory which is firmly rooted in Quantum Mechanics, applied directly to the electron density p and giving quantitative answers, is to be adopted. Bader s Quantum Theory of Atoms in Molecules (QTAM) [14, 15] meets nicely all these requirements. Such a theory has also been recently applied to molecular crystals as a valid tool to rationalize and quantitatively detect crystal field effects on the molecular densities [16-18]. 

These observations may be rationalized by assuming that the polar functional group coordinates to the metal center in one or more intermediates along the RCM pathway (Scheme 17) [30b]. Such a Lewis-acid/Lewis-base interaction may assemble the reacting sites within the coordination sphere of the ruthenium and hence provide internal bias for cyclization (e.g. structure I). However, if such an... 

Inhibition of H2 formation can be seen when the anode-volume is saturated with O2 application of an external bias up to 0.7 V can usually prevent this effect, increased yield of H2 when Pt is present as a cathode has been rationalized in terms of three factors (a) the removal of conduction band electron from Ti02 to Pt [equation (4.4.14)], (b) The ease of reactions (4.4.15) and (4.4.16) because of a low overpotential for H2 evolution from water at the Pt cathode, and (c) H atom migration to the Pt cathode. 

Whatever may be thought of self-deception, nobody doubts that wishes do sometimes bias rational thought-processes. But why do they bias them Truth seems to be an overriding goal and it is surely obvious that rationality gives us our best chance of attaining it. 

The conformational equilibria for the various alkyl substituted derivatives of 466 and 467 may also be rationalized in terms of nonbonded interactions and the generalized anomeric effect. Thus, the ring A alkyl substituted derivatives show heavy bias towards a particular conformation. Those isomers in which the substituent is equatorial in the trans-conformation, such as 482 and 483, show no detectable amounts of... 

---