Intermolecular forces stretching force constant

Fig. 19 Variation of the intermolecular stretching force constant ka with nucleophilicity Nb for several series of halogen-bonded complexes B- XY, where B is one of a series of Lewis bases and XY is Cl2, Br2, BrCl, C1F or IC1. N% were assigned by use of Eq. 4 with the choice of ICi = 10.0, hence the perfect straight line for the B- -IC1 series. The lines for the other series are those obtained by least-squares fits to the ka values using the Mb determined from the B- IC1 series. Points for E P- -IC1, E N- -C1F and EEN- BrCl are anomalous and were excluded from the fits (see text for discussion)... 

Evidence for a significant contribution from the ionic form [BX] + - -Y in a gas-phase complex B- XY was first deduced from the spectroscopic constants of H3N- -ClF, as obtained by analysis of its rotational spectrum [63]. In particular, the value ka = 34.3 N m 1 of the intermolecular stretching force constant (obtained from the centrifugal distortion constant Dj in the man-... 

The second well-known electrophilicity or nucleophilicity scale was by Legon and Millen [13,14]. In this scale, the assigned intrinsic nucleophilicity is derived from the intermolecular stretching force constant k, recorded from the rotational and infrared (IR) spectra of the dimer B. .. HX formed by the nucleophile B and a series of HX species (for X halogens) and other neutral electrophiles. The nucleophilicity number in this case is obtained from the empirical relation... 

Two classical tools, the intermolecular stretching force constants of H-bonded complexes and the molecular electrostatic potential, were used to develop a nucleophilicity index, which was validated against kinetic data recorded for the aminolysis of S-methyl 2,4-dinitrophenylthiocarbamate.51 Aminolysis of iV-phenylthionocarbamates by ben-zylamines in MeCN proceeded by a stepwise mechanism in which the rate-determining step was the breakdown of the zwitterionic tetrahedral intermediate.52... 

For characterizing a dipolar molecule in its electronic ground state, few methods are more instructive than pulsed-nozzle Fourier-trans-form microwave spectroscopy (32). As illustrated schematically in Fig. 5, a short pulse of microwave radiation directed at the gas pulse excites a rotational transition in the species of interest subsequently the rotationally excited molecules reemit radiation, which is detected. This technique provides a remarkably sensitive probe for transients, the properties of which can be specified with all the precision and detail peculiar to rotational spectroscopy only microseconds after their production. In relation to a weakly bound adduct A --B formed by two molecular reagents A and B, for example, we may draw on the rotational spectrum to determine such salient molecular properties as symmetry, radial and angular geometry, the intermolecular stretching force constant and internal dynamics, the electric charge distribution, and the electric dipole and quadrupole moments of A -B (see Table I). 

K Stretching force constant of an intermolecular bond of a weakly bound complex... 

Observed and calculated intermolecular stretching force constants fc,(Nm HX ... 

Another empirical equation has been established to predict the strength of hydrogen bonds between small amphoteric molecules such as H2O, HF, HCl, HBr, HC=N, HCMIIH and NH3 [37], from the intermolecular stretching force constants. This equation can be used to quantify the spectroscopic observation that water is the HBA in its complexes with HCl, HBr, HON and HCM h and is the HBD with NH3. 

Table 5.1 Intermolecular stretching force constants (k , N m j for dimers B- -X—Y [10],...

Figure 5.4 Comparison of intermolecular stretching force constants hydrogen bond versus halogen bond.

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