Dynamical dipole

For NHj the orientational energy is quite large. However, since in the ground state the permanent dipole is perpendicular to the surface, the dynamical dipole for this mode is zero, so that the mode is EELS-lnactlve. 

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. 

Saue and Jensen used linear response theory within the random phase approximation (RPA) at the Dirac level to obtain static and dynamic dipole polarizabilities for Cu2, Ag2 and Au2 [167]. The isotropic static dipole polarizability shows a similar anomaly compared with atomic gold, that is, Saue and Jensen obtained (nonrelativ-istic values in parentheses) 14.2 for Cu2 (15.1 A ), 17.3 A for Ag2 (20.5 A ), and 12.1 A for Au2 (20.2 A ). They also pointed out that relativistic and nonrelativistic dispersion curves do not resemble one another for Auz [167]. We briefly mention that Au2 is metastable at 5 eV with respect to 2 Au with a barrier to dissociation of 0.3 eV [168, 169]. 

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. 

In general, when using unpolarized light, the vibrations both parallel and perpendicular to the interface are excited. However, when the light is polarized, selected dynamic dipoles are excited, from which the orientation of the dipoles can be inferred. 

In an effort to understand the mechanisms involved in formation of complex orientational structures of adsorbed molecules and to describe orientational, vibrational, and electronic excitations in systems of this kind, a new approach to solid surface theory has been developed which treats the properties of two-dimensional dipole systems.61,109,121 In adsorbed layers, dipole forces are the main contributors to lateral interactions both of dynamic dipole moments of vibrational or electronic molecular excitations and of static dipole moments (for polar molecules). In the previous chapter, we demonstrated that all the information on lateral interactions within a system is carried by the Fourier components of the dipole-dipole interaction tensors. In this chapter, we consider basic spectral parameters for two-dimensional lattice systems in which the unit cells contain several inequivalent molecules. As seen from Sec. 2.1, such structures are intrinsic in many systems of adsorbed molecules. For the Fourier components in question, the lattice-sublattice relations will be derived which enable, in particular, various parameters of orientational structures on a complex lattice to be expressed in terms of known characteristics of its Bravais sublattices. In the framework of such a treatment, the ground state of the system concerned as well as the infrared-active spectral frequencies of valence dipole vibrations will be elucidated. 

Our concern here is with the periodic orientations of dynamic dipole moments, when a unit cell of a two-dimensional crystal may be thought of as containing n orientationally inequivalent molecules ... 

In the particular case of dipole-dipole lateral interactions between molecules with the same dynamic dipole moment //, we have ... 

Here we focus on the effect of dipolar dispersion laws for high-frequency collective vibrations on the shift and width of their spectral line, with surface molecules inclined at an arbitrary angle 6 to the surface-normal direction. For definiteness, we consider the case of a triangular lattice and the ferroelectric ordering of dipole moments inherent in this lattice type.56,109 Lateral interactions of dynamic dipole moments p = pe (e = (sin os, sin6fcin , cos )) corresponding to collective vibrations on a simple two-dimensional lattice of adsorbed molecules cause these vibrations to collectivize in accordance with the dispersion law 121... 

Polymer films were produced by surface catalysis on clean Ni(100) and Ni(lll) single crystals in a standard UHV vacuum system H2.131. The surfaces were atomically clean as determined from low energy electron diffraction (LEED) and Auger electron spectroscopy (AES). Monomer was adsorbed on the nickel surfaces circa 150 K and reaction was induced by raising the temperature. Surface species were characterized by temperature programmed reaction (TPR), reflection infrared spectroscopy, and AES. Molecular orientations were inferred from the surface dipole selection rule of reflection infrared spectroscopy. The selection rule indicates that only molecular vibrations with a dynamic dipole normal to the surface will be infrared active [14.], thus for aromatic molecules the absence of a C=C stretch or a ring vibration mode indicates the ring must be parallel the surface. 

An important consequence of the presence of the metal surface is the so-called infrared selection rule. If the metal is a good conductor the electric field parallel to the surface is screened out and hence it is only the p-component (normal to the surface) of the external field that is able to excite vibrational modes. In other words, it is only possible to excite a vibrational mode that has a nonvanishing component of its dynamical dipole moment normal to the surface. This has the important implication that one can obtain information by infrared spectroscopy about the orientation of a molecule and definitely decide if a mode has its dynamical dipole moment parallel with the surface (and hence is undetectable in the infrared spectra) or not. This strong polarization dependence must also be considered if one wishes to use Eq. (1) as an independent way of determining ft. It is necessary to put a polarizer in the incident beam and use optically passive components (which means polycrystalline windows and mirror optics) to avoid serious errors. With these precautions we have obtained pretty good agreement for the value of n determined from Eq. (1) and by independent means as will be discussed in section 3.2. 

An ordered monolayer of molecules having a large dynamical dipole moment must not be regarded as an ensemble of individual oscillators but a strongly coupled system, the vibrational excitations being collective modes (phonons) for which the wavevector q is a good quantum number. The dispersion of the mode for CO/Cu(100) in the c(2 x 2) structure has been measured by off-specular EELS, while the infrared radiation of course only excites the q = 0 mode. 

In conclusion, the effects of the dipole-dipole interaction cause the greatest difference between the interpretation of infrared spectra of gas phase and adsorbed molecules and if the mode has a large dynamical dipole moment this interaction is always in operation. 

In section 3.1 we discussed the present picture of the electronic arrangement of CO chemisorbed on a metal surface, which was schematically shown in Fig. 3. When the molecule is vibrationally excited charge is oscillating between the 2n resonance and the metal. This gives rise to the large increase in the dynamical dipole moment, as was discussed in that section. These local charge... 

Fig. 18. Infrared spectra of C -H vibrations of different coverages of CH30 on Cu(lOO) at 100K, showing the symmetric (at 2800cm ) and two asymmetric stretch modes. Inset shows a tilted chemisorbed methoxide molecule and the orientations of the dynamical dipole moments ji. (Reproduced by permission from...

When Jens Oddershede was elected a Fellow of the American Physical Society in 1993, the citation read For contribution to the theory, computation, and understanding of molecular response properties, especially through the elucidation implementation of the Polarization Propagator formalism. Although written more than a decade ago, it is still true today. The common thread that has run through Jens work for the past score of years is development of theoretical methods for studying the response properties of molecules. His primary interest has been in the development and applications of polarization propagator methods for direct calculation of electronic spectra, radiative lifetime and linear and non-linear response properties such as dynamical dipole polarizabilities and... 

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