Relaxation, vibrational adiabatic effects

E.E.Nikitin, Non-adiabatic effects in collisional vibrational relaxation of diatomic molecules, in The Physics of Electronic and Atomic Collisions, ed. J.S.Risley, R.Geball, University of Washington Press, Seattle and London, 1975... 

Transient vibrational dynamics. Perturbation theory yields an intuitive picture of adsorbate relaxation the loss of a vibrational quantum and associated nodal structure in the nuclear wave function is coupled to an irreversible transfer of momentum to the metallic electrons (see Fig. 2). To obtain time-resolved information about the dynamical processes at work, it is nonetheless necessary to go beyond this simple model. In the past decades, classical molecular dynamics has been hugely successful at shedding light on the transient vibrational evolution in a variety of adsorbate-surface systems (see, e.g., ref. 54-56). The methods of choice for including non-adiabatic effects on the dynamics can be divided in two main families friction-lype... 

Rapid aerodynamic flow past obstacles involves adiabatic compressions and rarefactions, and is influenced by relaxation of internal degrees of freedom in a way similar to shock phenomena. This effect has been quantitatively treated by Kan-trowitz18, who developed a method for obtaining relaxation times by measuring the pressure developed in a small Pitot tube which forms an obstacle in a rapid gas stream. This impact tube is not a very accurate technique, and requires a very large amount of gas it has been used to obtain a vibrational relaxation time for steam. 

It should be noted that relation (2.51) is valid within the sudden approximation. However, the relaxation of heavy particle impurities typically involves motion that is slow compared with vibrations of the host lattice (i.e., the tunneling takes place in the adiabatic limit). The net effect of the adiabatic approximation is to renormalize the effective moment of inertia of the particle. This approach was used, for example, to describe vacancy diffusion in light metals. The evolution of the rate constant from Arrhenius behavior to the low-temperature plateau was described within the framework of one-dimensional tunneling of a... 

In contrast to the subsystem representation, the adiabatic basis depends on the environmental coordinates. As such, one obtains a physically intuitive description in terms of classical trajectories along Born-Oppenheimer surfaces. A variety of systems have been studied using QCL dynamics in this basis. These include the reaction rate and the kinetic isotope effect of proton transfer in a polar condensed phase solvent and a cluster [29-33], vibrational energy relaxation of a hydrogen bonded complex in a polar liquid [34], photodissociation of F2 [35], dynamical analysis of vibrational frequency shifts in a Xe fluid [36], and the spin-boson model [37,38], which is of particular importance as exact quantum results are available for comparison. 

Pump-probe experiment is an efficient approach to detect the ultrafast processes of molecules, clusters, and dense media. The dynamics of population and coherence of the system can be theoretically described using density matrix method. In this chapter, for ultrafast processes, we choose to investigate the effect of conical intersection (Cl) on internal conversion (IC) and the theory and numerical calculations of intramolecular vibrational relaxation (IVR). Since the 1970s, the theories of vibrational relaxation have been widely studied [1-7], Until recently, the quantum chemical calculations of anharmonic coefficients of potential-energy surfaces (PESs) have become available [8-10]. In this chapter, we shall use the water dimer (H20)2 and aniline as examples to demonstrate how to apply the adiabatic approximation to calculate the rates of vibrational relaxation. 

In the following section, the importance of metallic non-adiabaticity in chemical dynamics simulations will be illustrated through a few selected example applications. First, the vibrational relaxation of adsorbates at metallic surfaces will be treated in the perturbative regime. Seeond, the effect of weak non-adiabatic coupling on laser excitation simulations will be discussed. Finally, inelastic effects in scanning tunnelling mieroseopy of highly mobile species in metallic environments will be diseussed in terms of non-adiabaticity. 

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