Vibrational molecular excitation

Conventional spontaneous Raman scattering is the oldest and most widely used of the Raman based spectroscopic methods. It has served as a standard teclmique for the study of molecular vibrational and rotational levels in gases, and for both intra- and inter-molecular excitations in liquids and solids. (For example, a high resolution study of the vibrons and phonons at low temperatures in crystalline benzene has just appeared [38].)... 

EELS Electron energy loss spectroscopy The loss of energy of low-energy electrons due to excitation of lattice vibrations. Molecular vibrations, reaction mechanism... 

Figure B2.5.18 compares this inter molecular selectivity with intra molecular or mode selectivity. In an IR plus UV, two-photon process, it is possible to break either of the two bonds selectively in the same ITOD molecule. Depending on whether the OFI or the OD stretching vibration is excited, the products are either IT -t OD or FIO + D [24]- hr large molecules, mirmnolecular selectivity competes with fast miramolecular (i.e. unimolecular) vibrational energy redistribution (IVR) processes, which destroy the selectivity. In laser experiments with D-difluorobutane [82], it was estimated that, in spite of frequency selective excitation of the...

Molecular excitation by light absorption takes place during the period of one vibration of the exciting light wave. For light with a wavelength A equal to 300 nanometers (nm), this corresponds to 10"15 sec ... 

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. 

Where infrared and Raman spectroscopy are limited to vibrations in which a dipole moment or the molecular polarizability changes, EELS detects all vibrations. Two excitation mechanisms play a role in EELS dipole and impact scattering. 

We have also learned that VMP is an effective tool in molecular spectroscopy and molecular dynamics studies. It is effective, in particular, for determination of IVR lifetimes and for studying the vibrational spectroscopy of states that are difficult to study applying other methods. The above-mentioned limit of the size of the molecule is irrelevant here. For observing the mode selectivity in VMP, the vibrational excitation has to survive IVR in order to retain the selectivity since the subsequent electronic excitation has to be from the excited vibrational state. In contrast, monitoring vibrational molecular dynamics relies only on the efficacy of the excitation of the specific rovibrational state. When IVR is fast and rovibrational distribution reaches equilibrium, the subsequent electronic excitation will still reflect the efficacy of the initial rovibrational excitation. In other words, whereas fast IVR precludes mode selectivity, it facilitates the unraveling of the vibrational molecular dynamics. 

Chemical reactivity of vibrationally excited molecules may be much higher than for the same species in thermal equilibrium. Although direct IR excitation is limited by the choice of lasers available and usually lends itself predominantly to the excitation of the first few vibrational levels and to IR active transitions,2, 3 no such restriction applies to molecular excitation by E-V-R transfer. 

If the mechanical degrees of freedom are coupled strongly to the environment (dissipative vibron), then the dissipation of molecular vibrations is determined by the environment. However, if the coupling of vibrations to the leads is weak, we should consider the case when the vibrations are excited by the current flowing through a molecule, and the dissipation of vibrations is also determined essentially by the coupling to the electrons. Here, we show that the effects of vibron emission and vibronic instability are important especially in the case of electron-vibron resonance. 

Figure 10 A typical trajectory showing rotational excitation accompanying vibrational de-excitation (i.e. a vibration to rotational energy transfer) [71]. The top panel shows the evolution in the Z (molecule-surface distance) and r (molecular bond length) coordinates. In the lower panel, the motion is projected onto the r — 0 (molecular bond orientation) plane. Coupling of vibrations and rotations occurs because the molecule attempts to dissociate at an unfavourable bond angle.

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