Hydrogen bonding spectral densities

The linear response theory [50,51] provides us with an adequate framework in order to study the dynamics of the hydrogen bond because it allows us to account for relaxational mechanisms. If one assumes that the time-dependent electrical field is weak, such that its interaction with the stretching vibration X-H Y may be treated perturbatively to first order, linearly with respect to the electrical field, then the IR spectral density may be obtained by the Fourier transform of the autocorrelation function G(t) of the dipole moment operator of the X-H bond ... 

Figure 13. Hydrogen bond involving a Fermi resonance relative influence of the damping parameters. Spectral densities 7sf(co) computed from Eq. (81). Common parameters a0 = 1, A = 160cm-1, co0 = 3000cm-1, co00 = 150cm-1, 2t05 = 2790cm-1, and T = 300K.

In the presence of both order-disorder and displacive, as in the KDP family, the two dynamic concepts have somehow to be merged. It could well be that the damping constant Zs becomes somewhat critical too (at least in the over-damped regime of the soft mode), because of the bihnear coupling of r/ and p. It would, however, lead too far to discuss this here in more detail. The corresponding theory of NMR spin-lattice relaxation for the phase transitions in the KDP family has been worked out by Blinc et al. [19]. Calculation of the spectral density is here based on a collective coordinate representation of the hydrogen bond fluctuations connected with a soft lattice mode. Excellent and comprehensive reviews of the theoretical concepts, as well as of the experimental verifications can be found in [20,21]. 

The MD simulations show that second shell water molecules exist and are distinct from freely diffusing bulk water. Freed s analytical force-free model can only be applied to water molecules without interacting force relative to the Gd-complex, it should therefore be restricted to water molecules without hydrogen bonds formed. Freed s general model [91,92] allows the calculation of NMRD profiles if the radial distribution function g(r) is known and if the fluctuation of the water-proton - Gd vector can be described by a translational motion. The potential of mean force in Eq. 24 is obtained from U(r) = -kBT In [g(r)] and the spectral density functions have to be calculated numerically [91,97]. 

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