Molecules angular momentum

We consider an isolated molecule in field-free space with Hamiltonian //. We let Pbe the total angular momentum operator of the molecule, that is... 

We hope that by now the reader has it finnly in mind that the way molecular symmetry is defined and used is based on energy invariance and not on considerations of the geometry of molecular equilibrium structures. Synnnetry defined in this way leads to the idea of consenntion. For example, the total angular momentum of an isolated molecule m field-free space is a conserved quantity (like the total energy) since there are no tenns in the Hamiltonian that can mix states having different values of F. This point is discussed fiirther in section Al.4.3.1 and section Al.4.3.2. 

A specific unimolecular rate constant for the decay of a highly excited molecule at energy E and angular momentum J takes the fomr... 

There are significant differences between tliese two types of reactions as far as how they are treated experimentally and theoretically. Photodissociation typically involves excitation to an excited electronic state, whereas bimolecular reactions often occur on the ground-state potential energy surface for a reaction. In addition, the initial conditions are very different. In bimolecular collisions one has no control over the reactant orbital angular momentum (impact parameter), whereas m photodissociation one can start with cold molecules with total angular momentum 0. Nonetheless, many theoretical constructs and experimental methods can be applied to both types of reactions, and from the point of view of this chapter their similarities are more important than their differences. 

The simplest case is a transition in a linear molecule. In this case there is no orbital or spin angular momentum. The total angular momentum, represented by tire quantum number J, is entirely rotational angular momentum. The rotational energy levels of each state approximately fit a simple fomuila ... 

Spin-rotation 1 Reorientation and time dependence of angular momentum Small molecules only [M... 

When the molecule is not in a S state there is an interaction between the rotation of the molecule and S and/or L, and the details of coupling the angular momenta are involved. Most nonsinglet molecules with electronic orbital angular momentum A = 0 obey Hund s case (b) coupling. In Case (b), the electronic orbital angular momentum combines with the nuclear orbital angular... 

Suppose that W(r,Q) describes the radial (r) and angular (0) motion of a diatomic molecule constrained to move on a planar surface. If an experiment were performed to measure the component of the rotational angular momentum of the diatomic molecule perpendicular to the surface (Lz= -ih d/dQ), only values equal to mh (m=0,1,-1,2,-2,3,-3,...) could be observed, because these are the eigenvalues of ... 

The angles 0, (j), and x are the Euler angles needed to specify the orientation of the rigid molecule relative to a laboratory-fixed coordinate system. The corresponding square of the total angular momentum operator fl can be obtained as... 

When the three principal moment of inertia values are identical, the molecule is termed a spherical top. In this case, the total rotational energy can be expressed in terms of the total angular momentum operator J2... 

The rotational eigenfunctions and energy levels of a molecule for which all three principal moments of inertia are distinct (a so-called asymmetric top) can not easily be expressed in terms of the angular momentum eigenstates and the J, M, and K quantum numbers. However, given the three principal moments of inertia la, Ib, and Ic, a matrix representation of each of the three contributions to the rotational Hamiltonian... 

This completes our introduction to the subject of rotational and vibrational motions of molecules (which applies equally well to ions and radicals). The information contained in this Section is used again in Section 5 where photon-induced transitions between pairs of molecular electronic, vibrational, and rotational eigenstates are examined. More advanced treatments of the subject matter of this Section can be found in the text by Wilson, Decius, and Cross, as well as in Zare s text on angular momentum. 

This completes our introduction to the subject of molecular spectroscopy. More advanced treatments of many of the subjects treated here as well as many aspects of modern experimental spectroscopy can be found in the text by Zare on angular momentum as well as in Steinfeld s text Molecules and Radiation, 2 Edition, by J. I. Steinfeld, MIT Press (1985). 

Figure 5.5 The rotational angular momentum vector P for (a) a linear molecule and (b) the prolate symmetric rotor CH3I where is the component along the a axis...

Figure 5.12 shows the J= — 0 transition of the linear molecule cyanodiacetylene (H—C=C—C=C—C=N) observed in emission in Sagittarius B2 (Figure 5.4 shows part of the absorption spectrum in the laboratory). The three hyperfine components into which the transition is split are due to interaction between the rotational angular momentum and the nuclear spin of the nucleus for which 1= 1 (see Table 1.3). The vertical scale is a measure of the change of the temperature of the antenna due to the received signal. 

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