AMI calculations

Table 8—1. Heats of formation of selected m olecules from AMI calculations...

The molecular dipole moment is perhaps the simplest experimental measure of charge density in a molecule. The accuracy of the overall distribution of electrons in a molecule is hard to quantify, since it involves all of the multipole moments. Experimental measures of accuracy are necessary to evaluate results. The values for the magnitudes of dipole moments from AMI calculations for a small sample of molecules (Table 4) indicate the accuracy you may... 

Aromatic stabilization in kcal/mol based on semlempirical AMI calculations. ... 

We will perform an AMI calculation on tetraphenylporphin (TPP), pictured at right, in order to examine the four important molecular orbitals for this molecule the second-highest and highest occupied MO s and the lowest and second-lowest unoccupied MO s (which we denote HOMO-1, HOMO, LUMO and LUMO-ll, respectively). 

AMI calculations give a different stability order (AAHf = -2.3 kcal/mol). It was remarked that because of the high dipole moment of 111 =... 

Theoretical studies of the relative stabilities of tautomers 14a and 14b were carried out mostly at the semiempirical level. AMI and PM3 calculations [98JST(T)249] of the relative stabilities carried out for a series of 4(5)-substituted imidazoles 14 (R = H, R = H, CH3, OH, F, NO2, Ph) are mostly in accord with the conclusion based on the Charton s equation. From the comparison of the electronic spectra of 4(5)-phenylimidazole 14 (R2 = Ph, R = R3 = H) and 2,4(5)-diphenylimidazole 14 (R = R = Ph, R = H) in ethanol with those calculated by using ir-electron PPP method for each of the tautomeric forms, it follows that calculations for type 14a tautomers match the experimentally observed spectra better (86ZC378). The AMI calculations [92JCS(P1)2779] of enthalpies of formation of 4(5)-aminoimidazole 14 (R = NH2, R = R = H) and 4(5)-nitroimidazole 14 (R = NO2, R = R = H) point to tautomers 14a and 14b respectively as being energetically preferred in the gas phase. Both predictions are in disagreement with expectations based on Charton s equation and the data related to basicity measurements (Table III). These inconsistencies may be... 

These findings accord with the semiempirical AMI calculations [92JCS(P1)2779] of the heats of formation of all theoretically possible tautomeric forms of 4-aminoimidazole 53. The most stable are the tautomers 53a AHf = 213 kJ mol ) and 53d AHf = 215 kJ mol ) (Scheme 29). All... 

The ratio of the two diastereomeric products 190 and 191 was found to depend on the reaction temperature and reaction time. The addition of acrolein or methyl vinyl ketone proceeded smoothly, but in the case of methylacrylate or acrylonitrile the reaction did not proceed under the same conditions (EtsN THF 30°C). An accompanying AMI calculation of these Q ,/3-unsaturated compounds [LUMOs for acrolein, -0.13877 for methyl vinyl ketone, -0.06805 (s-trans) for methyl acrylate, -0.01413 (s-tmns) for acrylonitrile, 0.04971] suggested the low reactivity of methyl acrylate and acrylonitrile toward the Michael reaction (99H1321). 

The asymmetric synthesis of (4i ,9S, 9ai )-4-phenyl-l-trimethylsilyloxy-9-vinylperhydropyrido[2,l-c][l,4]oxazine by a high level of stereoselectivity in the cyclization of (3i ,5i )-5-phenyl-3-phenylsulfanyl-4-(6-trimethylsila-nylhex-4-enyl)-2-trimethylsilyloxymorpholine was rationalized via AMI calculations (98T10309). 

AMI Calculations of the potential energy surface of the photoisomerization of the hypothetical (V-imide 6 (R1 = CHO R2 = H) have been reported.78... 

Coxon et al. also reported that AMI calculation of the transition states for the reactions between ethylene and 5-methylcyclopentadienes 45-49 bearing the... 

Table 5 AMI Calculation of the transition states in Diels-Alder reactions between 5-X-pentamethylcyclopentadiones and maleic anhydride...

Prehminary AMI calculations carried out with the MOPAC program on 18 and related molecules suggest that there are atomic orbital contributions from the heteroatom (e.g., S in 18) to the frontier molecular orbitals. It is conceivable, therefore, that there is negative hyper conjugation involving specific orbitals of S and the P centers in 18. This electronic effect may explain the unusual stabiUty towards oxidation of 18 and other heteroatom functionaUzed primary bisphosphines as described above [51]. 

Intramolecular reactions usually dominate intermolecular addition for favorable ring sizes. Semiempirical (AMI) calculations found the intramolecular TS favorable to a comparable intermolecular reaction.68 (See Figure 4.1) The intramolecular TS, which is nearly 4 kcal/mol more stable, is quite productlike with a C—O bond distance of 1.6 A, and a bond order of 0.62. The bromonium ion bridging is unsymmetrical and fairly weak. The bond parameters for the intra- and intermolecular TSs are quite similar. 

Quantum chemical (AMI) calculations were performed on 24-cis and 2A-trans showing that the cA-isomer is more stable. The structures 24-cis and 24-trans represent the energetically favored conformers <1998H(48)1851>. 

AMI Calculated Charge Distribution (e) and Frontier Orbital Energies ( ) and Coefficients for 4- and 5-Aminoimidazoles (179) and (180)... 

AMI Calculated Properties of Some Electrophilic Reagents and Related Species... 

It may be noted that simple MOPAC AMI calculations suggest that the dipole moment of NOBOW is oriented antiparallel to the molecular arrow. As indicated in Figure 8.25, this means that for an up field, the molecular arrows are pointing down. Given the definition of the sign of P in FLCs, this also means that domains of the ShiCaPa phase with positive chirality have negative ferroelectric polarization, and vice versa. 

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