Trans conformation calculations

RB3LYP calculations indicate that the s-cis conformer of peroxy acids is more stable than the s-trans conformer. Calculations on the reaction of prop-2-enol with some peroxy acids showed that trans-transition states collapse to the epoxide via a 1,2-shift, whereas a 1,4-shift is operable for cis-transition states.195 Quantum mechanical calculations have been performed on the migration step of the Baeyer-Villiger rearrangements of some substituted acetophenones with m-chloroperbenzoic acid (m-CPBA). The energy barriers, charge distributions and frontier molecular orbitals, determined for the aryl migration step, have been used to explain the effects of substituents on the reactivity of the ketones.196... 

The conformation of the iV,iV-dimethyIaminopropyl side chain in CPZ HCl was found to be solvent dependent. The percent trans conformer calculated from the parameter N= J+f for each CH2CH2 fragment following the approach of Abraham ef are summarized in Table 4. The population of trans conformer for the C -C fragment was found to decrease drastically in water and in chloroform solutions, although the Cp-Cy fragment was predominantly trans in all three solvents. The side... 

With all-atom simulations the locations of the hydrogen atoms are known and so the order parameters can be calculated directly. Another structural property of interest is the ratio of trans conformations to gauche conformations for the CH2—CH2 bonds in the hydrocarbon tail. The trans gauche ratio can be estimated using a variety of experimental techniques such as Raman, infrared and NMR spectroscopy. 

The barrier for conversion of the skew conformation to the s-trans conformation is 3.9kcal/mol. This energy maximum presiunably refers to the conformation (transition state) in which the two n bonds are mutually perpendicular. Various MO calculations find the s-trans conformation to be 2-5 kcal/mol lower in energy than either the planar or skew cisoid conformations. Most high-level calculations favor the skew conformation over the planar s-cis, but the energy differences found are quite small. ... 

We ran an SCRF single point energy calculation for gauche dichloroethane conformers in cyclohexane (e=2.0), using the Onsager model at the Hartree-Fock and MP2 levels of theory (flfl=3.65) and using the IPCM model at the B3LYP level. The 6-31+G(d) basis set was used for all jobs. We also ran gas phase calculations for both conformations at the same model chemistries, and an IPCM calculation for the trans conformation (SCRF=Dipole calculations are not necessary for the trans conformation since it has no dipole moment). 

Hexahydropyiido[ 1,2-d -1,3,4-oxadiazines 212 may formally exist in three con-formers (Scheme 138) [99ACSA213]. However, according to simple Hartree-Fock calculations, the trans conformer 212c is the energetically preferred structure. 

Table 17 contains the enthalpies of activation and reaction for the three propagation steps in the gas phase and in solution. They were calculated by using classical cations possessing all-trans conformation. 

Vinylindoles have been studied extensively and used in the synthesis of carbazoles, alkaloids and other classes of pharmacologically active compounds. MMX force field calculations have shown that coplanar s-cis and. s-trans conformations of 3-vinylindole (84, Figure 2.11) are the most stable conformers they exhibit only slight differences in their thermodynamic stabilities [86]. 

The trisulfane molecule exists as two conformers which have been termed as cis- and trans-HzSi. While the trans-form is a helical molecule of C2 symmetry with the motif ++ (or — for the enantiomer), the cfs-form is of Q symmetry with the motif +- (identical to -+). Both forms have been detected by rotational spectroscopy [17, 45, 46]. The motif gives the order of the signs of the torsion angles at the SS bonds. The geometrical parameters [17] are presented in Table 4. The trans-isomer is by only 1 kj mol more stable than the cfs-form but the barrier to internal rotation from tmns to cis is 35 kJ mor [46]. The dipole moments were calculated by ab initio MO theory at the QCISD/TZ+P level as 0.68 D (trans) and 2.02 D (cis) [46]. For geometrical parameters of cis- and trans-trisulfane calculated at the MP2/6-311++G> > level, see [34]. 

Fig. 7. Conformations of substituted 4-lithio-l,3-dioxanes calculated at B3LYP/6-31-i-G(d)// HF/3-21G. Only the lowest energy 4,6-czs and 4,6-trans conformations are listed, along with the relative energy for each pair. The (4,6-czs)-5-axial conformation is 1.81 kcal/mol higher in energy than the (4,6-ds)-5-equatorial conformation...

Because of the difference in energy of these two groups, temperature changes alter the population of the two states. Ab initio calculations indicated [57,58] that the high-frequency peak is due to the trans conformation and the lower frequency peak to the cis conformation. Analysis of the relative band area gives the population of the two states as a function of temperature and hence allows... 

Independent of the contact geometry, the calculations also demonstrated that the introduction of gauche defects resulted in a decrease of the bridge conductance by a factor of 10, as compared to an all-trans alkanedithiol chain (see Fig. 14b, triangles). Due to variations in the number and positions of gauche defects, as well as various contact geometries, the molecular junctions can exhibit conductance values up to two orders of magnitude below the conductance values of an all-trans conformation of the alkyl chain. 

The ground state structure of butadiene has been extensively studied using different kinds of theoretical methods19,21,23,31,34,36. For this molecule, several conformations associated with rotation around the single C—C bond are possible. Experimental evidence shows that the most stable one is the planar s-trans conformation. All theoretical calculations agree with this fact. 

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