Dipoles 1,3, table

Table I. The dipole-dipole Table II. The dipole-quadrupole Table III. The quadrupole-quad-...

Obviously, is not zero but maintains a certain potential due to the interfacial dipoles. Table 5-1 shows the potential of zero charge for various metals in aqueous solution. The potenti d of zero charge appears to depend to some extent on the crystal plane of metal surfaces. 

Table 5.1. Comparison of binary spectral moments calculated from classical (C.), semi-classical (S.) and quantum (Q.) calculations, based on line shapes (.LS) and sum formulae (.SF), for He-Ar at 295 K. Moments computed from the classical line shape after desymmetrization procedures P-2 and P-4 (scaled) had been applied are also shown. Computations are based on the ab initio dipole, Table 4.3, and an advanced potential [12].

Most of the approaches outlined in Figure 15.10 have been successfully realized on insoluble supports, either with the alkene or alkyne linked to the support, or with support-bound 1,3-dipoles (Table 15.16). Nitrile oxides are highly reactive 1,3-dipoles and react smoothly with both electron-poor and electron-rich alkenes, including enol ethers [200]. The addition of resin-bound nitrile oxides to alkenes (Entries 5 and 6, Table 15.16) has also been accomplished enantioselectively under catalysis by diisopropyl tartrate and EtMgBr [201], The diastereoselectivity of the addition of nitrile oxides and nitrones to resin-bound chiral acrylates has been investigated [202], Intramolecular 1,3-dipolar cycloadditions of nitrile oxides and nitrones to alkenes have been used to prepare polycyclic isoxazolidines on solid phase (Entries 7 and 9, Table 15.16). 

A 1,3-dipole is a compound of the type a—Het—b that may undergo 1,3-dipolar cycloadditions with multiply bonded systems and can best be described with a zwitterionic all-octet Lewis structure. An unsaturated system that undergoes 1,3-dipolar cycloadditions with 1,3-dipoles is called dipolarophile. Alkenes, alkynes, and their diverse hetero derivatives may react as dipolarophiles. Since there is a considerable variety of 1,3-dipoles—Table 15.2 shows... 

An interesting addition to Huisgen s classical list of 18 1,3-dipoles (Table 6-1) are the cyclopropenone ketals, e.g., 6.9. Although known for more than two decades (Baucom and Butler, 1972), their mechanistic behavior and synthetic potential (e.g., for a synthesis of colchicine) was realized only by Boger and Brotherton-Pleiss (review 1990). Cyclopropenone ketals do not, however, belong to the scope of this volume. 

Dipole moments of diatomic molecules can be calculated directly. In more complex molecules, vector addition of the individual bond dipole moments gives the net molecular dipole moment. However, it is usually not possible to calculate molecular dipoles directly from bond dipoles. Table 3.8 shows experimental and calculated dipole moments of chloro-methanes. The values calculated from vectors use C—H and C—Cl bond dipole moments of 1.3 X 10 ° and 4.9 X 10 C m, respectively, and tetrahedral bond angles. Clearly, calculating dipole moments is more complex than simply adding the vectors for individual bond moments. However, for many purposes, a qualitative approach is sufficient. 

The time course of orientational changes induced by electric fields contains information on the orientation mechanism, and on the electrical and geometrical properties (main dipole axis, length) of the aligning and deorienting molecules. For instance, permanent dipole orientation of a given particle type in the presence of a constant electric field builds up with zero slope and has two modes, whereas the build-up of induced dipole orientation starts with maximum slope and is characterized by only one time constant. The deorientation relaxation of a system of identical particles, after termination of the step pulse, is monophasic, independently of the presence of permanent or induced dipoles. Table 3 summarizes the characteristic features of the rotational kinetics indicated by electric dichroism and birefringence for small perturbations. We see that there are a number of specific relationships to differentiate between permanent and induced dipole mechanism. In particular, the technique of field-reversal is a sensitive indicator for the relative contributions of permanent or induced dipoles. 

The main results from the preceding developments are the mounting rules, or Kirchhoff laws, that are recalled hereafter, but adapted to the case of N dipoles (Table 8.4). 

Interactions become shorter-ranged and weaker as higher multipole moments become involved. When a monopole interacts with a monopole. Coulomb s law says u r) oc r But when a monopole interacts with a distant dipole, coulombic interactions lead to u r) oc r (see Equation (21.26)). Continuing up the multipole series, two permanent dipoles that are far apart interact as u(r) oc r Such interactions can be either attractive or repulsive, depending on the orientations of the dipoles. Table 24.2 gives typical energies of some covalent bonds, and Table 24.3 compares covalent to noncovalent bond strengths. 

AIM properties can be quickly and easily calculated, including shape, volume [19], (r), (r ) (Table 2), and dipole (Table 3). For comparison, these properties are also given for free atoms and ions in Table S2. 

McClellan, A. L., Tables of Experimental Dipole Moments, W. H. Freeman, San Francisco (1963-74). 

The heat of immersion is measured calorimetrically with finely divided powders as described by several authors [9,11-14] and also in Section XVI-4. Some hi data are given in Table X-1. Polar solids show large heats of immersion in polar liquids and smaller ones in nonpolar liquids. Zetdemoyer [15] noted that for a given solid, hi was essentially a linear function of the dipole moment of the wetting liquid. 

McClellan A L 1963 Tables of Experimental Dipole Moments vol 1 (New York Freeman)... 

The SPC/E model approximates many-body effects m liquid water and corresponds to a molecular dipole moment of 2.35 Debye (D) compared to the actual dipole moment of 1.85 D for an isolated water molecule. The model reproduces the diflfiision coefficient and themiodynamics properties at ambient temperatures to within a few per cent, and the critical parameters (see below) are predicted to within 15%. The same model potential has been extended to include the interactions between ions and water by fitting the parameters to the hydration energies of small ion-water clusters. The parameters for the ion-water and water-water interactions in the SPC/E model are given in table A2.3.2. 

Phosphine is a colourless gas at room temperature, boiling point 183K. with an unpleasant odour it is extremely poisonous. Like ammonia, phosphine has an essentially tetrahedral structure with one position occupied by a lone pair of electrons. Phosphorus, however, is a larger atom than nitrogen and the lone pair of electrons on the phosphorus are much less concentrated in space. Thus phosphine has a very much smaller dipole moment than ammonia. Hence phosphine is not associated (like ammonia) in the liquid state (see data in Table 9.2) and it is only sparingly soluble in water. 

Molecular point-group symmetry can often be used to determine whether a particular transition s dipole matrix element will vanish and, as a result, the electronic transition will be "forbidden" and thus predicted to have zero intensity. If the direct product of the symmetries of the initial and final electronic states /ei and /ef do not match the symmetry of the electric dipole operator (which has the symmetry of its x, y, and z components these symmetries can be read off the right most column of the character tables given in Appendix E), the matrix element will vanish. 

The n ==> n transition thus involves ground Ai) and exeited Ai) states whose direet produet (Ai x Ai) is of Ai symmetry. This transition thus requires that the eleetrie dipole operator possess a eomponent of Ai symmetry. A glanee at the C2v point group s eharaeter table shows that the moleeular z-axis is of A symmetry. Thus, if the light s eleetrie field has a non-zero eomponent along the C2 symmetry axis (the moleeule s z-axis), the n ==> 71 transition is predieted to be allowed. Light polarized along either of the moleeule s other two axes eannot induee this transition. 

In eontrast, the n ==> 71 transition has a ground-exeited state direet produet of B2 X Bi = A2 symmetry. The C2v s point group eharaeter table elearly shows that the eleetrie dipole operator (i.e., its x, y, and z eomponents in the moleeule-fixed frame) has no eomponent of A2 symmetry thus, light of no eleetrie field orientation ean induee this n ==> 71 transition. We thus say that the n ==> 71 transition is El forbidden (although it is Ml allowed). 

The calculated electronic distribution leads to an evaluation of the dipole moment of thiazole. Some values are collected in Table 1-7 that can be compared to the experimental value of 1.61 D (158). 

Dipole moments were calculated for a large number of thiazole derivatives the corresponding results are reported in Table 1-8. 

Table 1 3 lists the dipole moments of various bond types For H—F H—Cl H—Br and H—I these bond dipoles are really molecular dipole moments A polar molecule has a dipole moment a nonpolar one does not Thus all of the hydrogen halides are polar molecules To be polar a molecule must have polar bonds but can t have a shape that causes all the individual bond dipoles to cancel We will have more to say about this m Section 1 11 after we have developed a feeling for the three dimensional shapes of molecules... 

The bond dipoles m Table 1 3 depend on the difference m electronegativity of the bonded atoms and on the bond distance The polarity of a C—H bond is relatively low substantially less than a C—O bond for example Don t lose sight of an even more important difference between a C—H bond and a C—O bond and that is the direction of the dipole moment In a C—H bond the electrons are drawn away from H toward C In a C—O bond electrons are drawn from C toward O As we 11 see m later chap ters the kinds of reactions that a substance undergoes can often be related to the size and direction of key bond dipoles... 

For each of the following molecules that contain polar covalent bonds indicate the positive and negative ends of the dipole using the symbol -<- Refer to Table 1 2 as needed... 

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... 

Tables. Dipole moments of selected molecules, from AMI calculations...

BOND AND GROUP DIPOLE MOMENTS Table 4.12 Bond Dipole Moments... 

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