Effective vibrational frequencies

Here, zcXg is the number of sites in the matrix from which atoms can jump onto the critical nucleus, vc is the effective vibrational frequency for such a jump, and G is the free energy of activation for the jump. 

Provided that the localized adsorption clearly prevails, it can be accounted for in a simple way — by introducing the effective vibration frequency vj c, which would make the mobile entropy equal to the localized one. From Eqs. 5.64 and 5.65 it follows that ... 

Figure 9.20 reveals the mechanistic reason for the profound changes in the intramolecular dynamics in acetylene that occur near Nb = 10 (Ka = 3). The opposite sign anharmonicities of the cis- and trans-bending vibrations cause the effective vibrational frequencies for the cis and trans normal mode benders, ui + 2vx, to become equal near Ubend = 10,... 

This Section contains a short description of main results of the present theory for more details see Ref. 12. The following points merit attention, (i) The theojy predicts a value of 6.5 for the pH of water at T = 293 K and = 0.999 g/cm. It would be possible by choosing effective vibrational frequencies appropriately to find a closer agreement with experience. However this would not reflect the real limits of the theory. The magic... 

The peeks of IR spectra can be characterized by their effective vibrational frequencies end modes. 

The effect of the additional term 2c is to increase the effective vibrational frequency, coj, causing an increase in energy for each eigenstate except for when J = 0. This effect is called vibration-rotation coupling. 

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