Equation vibrations

Tabor M, Levine R D, Ben-Shaul A and Steinfeld J I 1979 Microscopic and macroscopic analysis of non-linear master equations vibrational relaxation of diatomic molecules Mol. Phys. 37 141-58... 

The potential energy function for a chemical bond is far more complex than a harmonic potential at high energies, as discussed in Chapter 3. However, near the bottom of the well, the potential does not look much different from the potential for a harmonic oscillator we can then define an effective force constant for the chemical bond. This turns out to be another problem that can be solved exactly by Schrodinger s equation. Vibrational energy is also quantized the correct formula for the allowed energies of a harmonic oscillator turns out to be ... 

The corresponding fiinctions i-, Xj etc. then define what are known as the normal coordinates of vibration, and the Hamiltonian can be written in tenns of these in precisely the fonn given by equation (AT 1.69). witli the caveat that each tenn refers not to the coordinates of a single particle, but rather to independent coordinates that involve the collective motion of many particles. An additional distinction is that treatment of the vibrational problem does not involve the complications of antisymmetry associated with identical fennions and the Pauli exclusion prmciple. Products of the nonnal coordinate fiinctions neveitlieless describe all vibrational states of the molecule (both ground and excited) in very much the same way that the product states of single-electron fiinctions describe the electronic states, although it must be emphasized that one model is based on independent motion and the other on collective motion, which are qualitatively very different. Neither model faithfully represents reality, but each serves as an extremely usefiil conceptual model and a basis for more accurate calculations. 

We will explore the effect of three parameters 2 -and < )> that is, the time delay between the pulses, the tuning or detuning of the carrier frequency from resonance with an excited-state vibrational transition and the relative phase of the two pulses. We follow closely the development of [22]. Using equation (Al.6.73). 

In contrast to the bimoleciilar recombination of polyatomic radicals ( equation (A3.4.34)1 there is no long-lived intennediate AB smce there are no extra intramolecular vibrational degrees of freedom to accommodate the excess energy. Therefore, the fonnation of the bond and the deactivation tlirough collision with the inert collision partner M have to occur simultaneously (within 10-100 fs). The rate law for trimoleciilar recombination reactions of the type in equation (A3.4.47) is given by... 

Although the Sclirodinger equation associated witii the A + BC reactive collision has the same fonn as for the nonreactive scattering problem that we considered previously, it cannot he. solved by the coupled-channel expansion used then, as the reagent vibrational basis functions caimot directly describe the product region (for an expansion in a finite number of tenns). So instead we need to use alternative schemes of which there are many. 

If the ratio of the products of vibrational frequencies is replaced by equation (A3,12,29) becomes... 

Another near resonant process is important in the hydrogen fluoride laser, equation (A3.13.37), where vibrational to vibrational energy transfer is of interest ... 

Vibrational motion is thus an important primary step in a general reaction mechanism and detailed investigation of this motion is of utmost relevance for our understanding of the dynamics of chemical reactions. In classical mechanics, vibrational motion is described by the time evolution and l t) of general internal position and momentum coordinates. These time dependent fiinctions are solutions of the classical equations of motion, e.g. Newton s equations for given initial conditions and I Iq) = Pq. 

Figure A3.13.15. Master equation model for IVR in highly excited The left-hand side shows the quantum levels of the reactive CC oscillator. The right-hand side shows the levels with a high density of states from the remaining 17 vibrational (and torsional) degrees of freedom (from [38]).

Section BT1.2 provides a brief summary of experimental methods and instmmentation, including definitions of some of the standard measured spectroscopic quantities. Section BT1.3 reviews some of the theory of spectroscopic transitions, especially the relationships between transition moments calculated from wavefiinctions and integrated absorption intensities or radiative rate constants. Because units can be so confusing, numerical factors with their units are included in some of the equations to make them easier to use. Vibrational effects, die Franck-Condon principle and selection mles are also discussed briefly. In the final section, BT1.4. a few applications are mentioned to particular aspects of electronic spectroscopy. 

Electronic spectra are almost always treated within the framework of the Bom-Oppenlieimer approxunation [8] which states that the total wavefiinction of a molecule can be expressed as a product of electronic, vibrational, and rotational wavefiinctions (plus, of course, the translation of the centre of mass which can always be treated separately from the internal coordinates). The physical reason for the separation is that the nuclei are much heavier than the electrons and move much more slowly, so the electron cloud nonnally follows the instantaneous position of the nuclei quite well. The integral of equation (BE 1.1) is over all internal coordinates, both electronic and nuclear. Integration over the rotational wavefiinctions gives rotational selection rules which detemiine the fine structure and band shapes of electronic transitions in gaseous molecules. Rotational selection rules will be discussed below. For molecules in condensed phases the rotational motion is suppressed and replaced by oscillatory and diflfiisional motions. 

Here each < ) (0 is a vibrational wavefiinction, a fiinction of the nuclear coordinates Q, in first approximation usually a product of hamionic oscillator wavefimctions for the various nomial coordinates. Each j (x,Q) is the electronic wavefimctioii describing how the electrons are distributed in the molecule. However, it has the nuclear coordinates within it as parameters because the electrons are always distributed around the nuclei and follow those nuclei whatever their position during a vibration. The integration of equation (Bl.1.1) can be carried out in two steps—first an integration over the electronic coordinates v, and then integration over the nuclear coordinates 0. We define an electronic transition moment integral which is a fimctioii of nuclear position ... 

This last transition moment integral, if plugged into equation (B 1.1.2). will give the integrated intensity of a vibronic band, i.e. of a transition starting from vibrational state a of electronic state 1 and ending on vibrational level b of electronic state u. 

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