Phonons multiphonon excitations

Figure 2 Vibrational energy relaxation (VER) mechanisms in polyatomic molecules, (a) A polyatomic molecule loses energy to the bath (phonons). The bath has a characteristic maximum fundamental frequency D. (b) An excited vibration 2 < D decays by exciting a phonon of frequency ph = 2. (c) An excited vibration >d decays via simultaneous emission of several phonons (multiphonon emission), (d) An excited vibration 2 decays via a ladder process, exciting lower energy vibration a> and a small number of phonons, (e) Intramolecular vibrational relaxation (IVR) where 2 simultaneously excites many lower energy vibrations, (f) A vibrational cascade consisting of many steps down the vibrational ladder. The lowest energy doorway vibration decays directly by exciting phonons. (From Ref. 96.)...

We have shown, in later sections, how precise INS measurements of the DOS provide the most stringent means of testing the model potential functions that lie at the heart of any LD or MD simulation. In the last a few years, we have systematically studied the vibrational dynamics of a large verity of phases of ice using above instruments at ISIS. These spectra were obtained at very low temperatures (< 15 K) on the recoverable high-pressure phases of ice and a few forms of amorphous forms of ice, in order to reduce the Debye-Waller factor and avoid multiphonon excitations. Hence the one-phonon spectra, g(co), can be extracted from the experimental data for the theoretical simulations. 

An alternative approach widely used in polyatomic molecule studies is based on the Golden Rule and a perturbative treatment of the anharmonic coupling (57,62). This approach is not much used for diatomic molecules. In the liquid O2 example cited above, the Hamiltonian must be expanded to 30th order or so to calculate the multiphonon emission rate. But for vibrations of polyatomic molecules, which can always find relatively low-order VER pathways for each VER step, perturbation theory is very useful. In the perturbation approach, the molecule s entire ladder of vibrational excitations is the system and the phonons are the bath. Only lower-order processes are ordinarily needed (57) because polyatomic molecules have many vibrations ranging from higher to lower frequencies and only a small number of phonons, usually one or two, are excited in each VER step. The usual practice is to expand the interaction Hamiltonian (qn, Q) in Equation (2) in powers of normal coordinates (57,62) ... 

Indirect transfer occurs by a two-part mechanism, as shown in Fig. 18. First a vibrational excitation decays by generating phonons. The phonons then produce vibrational excitation on other molecules by multiphonon up-pumping. Indirect transfer will not occur unless the density of vibrational excitations is large enough to produce a real increase in the bath temperature. 

The observation that the reaction requires an induction time of tens of picoseconds can be used to differentiate between proposed mechanisms of how shock wave energy localizes to cause chemical reaction. This induction time is expected for mechanisms that involve vibrational energy transfer, such as multiphonon up-pumping [107], where the shock wave excites low frequency phonons that multiply annihilate to excite the higher frequency modes involved in dissociation. It is also consistent with electronic excitation relaxing into highly excited vibrational states before dissociation, and experiments are underway to search for electronic excitations. On the other hand, prompt mechanisms, such as direct high frequency vibrational excitation by the shock wave, or direct electronic excitation and prompt excited state dissociation, should occur on sub-picosecond time scales, in contrast to the data presented here. 

Here g is the electron-lattice coupling constant, suffixes S and A are sensitizer and activator ions respectively, n is the number of phonons excited at the temperature of the system, hco is the phonon energy which contributes dominantly to these multiphonon processes and N is the number of phonons emitted in the processes, namely,... 

Ptutoyujum. (Am +). The energy level scheme and possible lasing transitions for Pu + are very similar to those of Np +. Prospective transitions include 6Hg/2+6H5/2, 9/2 7/2, and h7/2 Hc/2 For efficient fluorescence and laser action from either tne °Hg/2 or j/2 states, hosts should have low phonon frequencies to reduce nonradiative decay by multiphonon processes. Depending upon the host and the exact positions of higher-lying states, excited-state absorption may reduce or prevent net gain. 

Fig. 12. Experimental measurement of multiphonon up-pumping in nitromethane (NM), reproduced from ref. [127]. Phonons are generated using a picosecond pulse to excite a dye molecular heater. Anti-Stokes Raman spectroscopy is used to monitor population changes that can be converted to vibrational quasitemperatures. The 657 cm 1 doorway vibration is pumped faster than the instrument resolution of 25 ps. The 918 cm C-N stretch, which must be activated to break a C-N bond, is excited 25 ps later.

Most of the earlier theoretical studies dealt with the simplest relaxation mechanism where the internal vibrational energy of the guest is dissipated directly into the delocalized and harmonic lattice phonons. The common results of these works " were, as we mentioned above, predictions of a strong temperature dependence for the relaxation and an exponential decrease in the rates with the size of the vibrational frequency. The former result has its origin in stimulated phonon emission the conversion of vibrational energy into lattice phonons is greatly facilitated if some excited phonon states are thermally populated. The energy-gap law is due to the fact that the order of the multiphonon relaxation increases with the size of... 

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