Relaxed energy maps

Figure 4. Conformational map for dihydropyran. Because of the double bond, 4 atoms are always almost coplanar and a limited number of conformations is probable. The energy contours are at 2 kcal/mol intervals, starting 1 kcal/mol above the minima. The favored conformations are half-chairs, and the easiest paths of transition between the two are through the boat forms. The symmetry of this energy map applies only to dihydropyran, and not to derivatives which cause increases and decreases in the sizes of the allowed (low-energy) areas. This map was calculated with MMP2(85) at increments of 0.1 A shift of the two non-planar atoms. Three of the carbon atoms were held in a plane while C6 and 01 were held at specific distances above and below the plane. Otherwise, the structure was fully relaxed at each increment. The reader may enjoy plotting the indicated path of conformational interchange (pseudorotation) on a copy of Figure 3.

Figure 10. Relaxed (adiabatic) conformational energy map for p-maltose as computed by Brady and coworkers.i3 Contours are drawn at 2,4,6, 8, and 10 kcal/mol above the minimum near < ), y = -60°, -40°. The p-maltose structure may be derived from that of p-cellobiose in Fig. 1 by inversion of the stereochemical configuration at Cl.

Figure 5a. An example of a partial energy map, the local relaxed map for the S4 family of conformations. Contours are indicated at 4, 6, and 8 kcal/mol above the global SI minimum, which does not appear on this map. The dashed lines surround the different inter-residue hydrogen bond domains (with a cutoff criterion of 2.05A for the O. .. H distance), with the tic marks on the d hes pointing toward the region where the given hydrogen bond is allowed.

The relaxed conformational energy map for Ag-Ig with the IdoA ring in the form is shown in Figure 1. The map for the form... 

Is the decrease in activation energy sufficient to realize the existence of a crossing point in the relaxation time map If only the change of activation energy occurred, the crossing point in relaxation time map would be realized at extremely high temperature... 

INS results and ellipsometry results seem to be explained using the schematic sketch of the relaxation time map. INS measurements with different energy resolutions can serve as a self-check for the relaxation time map, and an increase in Tg would be expected with lowering the energy resolution for same sample. Returning to Fig. 22, it was confirmed that Tg increased with lowering energy resolution hence, the schematically prepared relaxation time map is consistent with our results. 

In order to construct a more reliable relaxation time map quantitatively, complementary use of other methods like dielectric relaxation measurements and INS measurements with different energy resolutions are still needed. 

Fig. 3. Projections on the (<1>, maps of the CICADA conformational search of the pentasaccharide. The dots indicate the values of all the optimized conformations determined by CICADA at each glycosidic linkange in 8 kcal/mol energy window For comparison, the isocontours, drawn in 1 Kcal/mol steps with an outer limit of 8 kcal/mol, represent the energy level of each disaccharide and calculated with the relaxed grid search approach. Dashed regions represent the locations of the low energy conformation of the pentasaccharide plotted on the potential energy surfaces of the constituting disaccharide segments...

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