Dipole moment dynamic

Figure 12. Plots of the binding energy ) . anharmonic vibrational fiequency static dipole moment dynamic dipole moment /to, Hitshfeld charge atom Pt clusters. Reprinted with permission from S. A. Wasileski eial.,J. Chem. Phys., 115, (2001) 8193. Copyright 2001, American Institute of Physics...

The reconstruction of the bandshape of the imidazole crystal was also performed using Car-Parrinello molecular dynamics (CPMD) simulation [73] of the unit cell of the crystal the results reproduce both the frequencies and intensities of the experimental IR spectrum of bands reasonably well, which we attribute to the application of dipole moment dynamics. The results are presented in Fig. 8 [70]. These and other recent CPMD calculations, on 2-hydroxy-5-nitrobenzamide crystal [71], oxalic acid dihydrate [72], and other systems [64-69], show that the CPMD method is adequate for spectroscopic investigations of complex systems with hydrogen bonds since it takes into account most of mechanisms determining the hydrogen bond dynamics (anharmonicity, couplings between vibrational modes, and intermolecular interactions in crystals). 

TIk experimentally determined dipole moment of a water molecule in the gas phase is 1.85 D. The dipole moment of an individual water molecule calculated with any of thv se simple models is significantly higher for example, the SPC dipole moment is 2.27 D and that for TIP4P is 2.18 D. These values are much closer to the effective dipole moment of liquid water, which is approximately 2.6 D. These models are thus all effective pairwise models. The simple water models are usually parametrised by calculating various pmperties using molecular dynamics or Monte Carlo simulations and then modifying the... 

The simplified theory is adequate to obtain qualitative agreement with experiment [1,16]. Comparisons between the simplified and more advanced versions of the theory show excellent agreement for the dominant (electronic) contribution to the time-dependent dipole moment, except during the initial excitation, where the k states are coupled by the laser field [17]. The contributions to the dipole from the heavy holes and light holes are not included in the simplified approach. This causes no difficulty in the ADQW because the holes are trapped and do not make a major contribution to the dynamics [1]. This assumption may not be valid in the more general case of superlattices, as discussed below. 

Stimulated by these observations, Odelius et al. [73] performed molecular dynamic (MD) simulations of water adsorption at the surface of muscovite mica. They found that at monolayer coverage, water forms a fully connected two-dimensional hydrogen-bonded network in epitaxy with the mica lattice, which is stable at room temperature. A model of the calculated structure is shown in Figure 26. The icelike monolayer (actually a warped molecular bilayer) corresponds to what we have called phase-I. The model is in line with the observed hexagonal shape of the boundaries between phase-I and phase-II. Another result of the MD simulations is that no free OH bonds stick out of the surface and that on average the dipole moment of the water molecules points downward toward the surface, giving a ferroelectric character to the water bilayer. 

In the "scissors mode" of H2O, the protons move parallel to the surface and the oscillation frequency is almost unaffected. For NH3, on the other hand, the so called "umbrella mode" is drastically stiffened by the surface because the protons move against the surface and suffer a strong Coulomb repulsion. Here again the dynamical dipole moment is dp/da = 2 Pj, slnda. For NHj, where Pjj = 0.53 a.u., the enhancement of the aynamlc dipole by the surface is compensated by the smaller oscillation amplitude. 

Mills calculated the enhancement of dynamic dipole moments for a dipole moment on a smooth silver or copper surface with a silver tip above it, which... 

Mills, D. L. (2002) Theory of STM -induced enhancement of dynamic dipole moments on crystal surfaces. Rhys. Rev. B, 65, 125419-1-125419-11. 

Cheng YM, Pu SC, Yu YC et al (2005) Spectroscopy and femtosecond dynamics of 7-N, N-diethylamino-3-hydroxyflavone. The correlation of dipole moments among various states to rationalize the excited-state proton transfer reaction. J Phys Chem A 109 11696-11706... 

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 ... 

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