Diatomic molecules angular momentum

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 ... 

We have seen in Chapters 1 and 5 that there is an angular momentum associated with end-over-end rotation of a diatomic molecule. In this section we consider only the non-rotating molecule so that we are concerned only with angular momenta due to orbital and spin... 

For diatomic molecules, there is coupling of spin and orbital angular momenta by a coupling scheme that is similar to the Russell-Saunders procedure described for atoms. When the electrons are in a specific molecular orbital, they have the same orbital angular momentum as designated by the m value. As in the case of atoms, the m value depends on the type of orbital. When the internuclear axis is the z-axis, the orbitals that form a bonds (which are symmetric around the internuclear axis) are the s, pz, and dzi orbitals. Those which form 7r bonds are the px, p, dlz, and dyi orbitals. The cip-y2 an(i dxy can overlap in a "sideways" fashion with one stacked above the other, and the bond would be a 8 bond. For these types of molecular orbitals, the corresponding m values are... 

A single particle of (reduced) mass p in an orbit of radius r = rq + r2 (= interatomic distance) therefore has the same moment of inertia as the diatomic molecule. The classical energy for such a particle is E = p2/2m and the angular momentum L = pr. In terms of the moment of inertia I = mr2, it follows that L2 = 2mEr2 = 2EI. The length of arc that corresponds to particle motion is s = rep, where ip is the angle of rotation. The Schrodinger equation is1... 

Judd, B. R. (1975), Angular Momentum Theory for Diatomic Molecules, Academic Press, New York. 

Figure 1. Translation, rotation, and vibration of a diatomic molecule. Every molecule has three translational degrees of freedom corresponding to motion of the center of mass of the molecule in the three Cartesian directions (left side). Diatomic and linear molecules also have two rotational degrees of freedom, about rotational axes perpendicular to the bond (center). Non-linear molecules have three rotational degrees of freedom. Vibrations involve no net momentum or angular momentum, instead corresponding to distortions of the internal structure of the molecule (right side). Diatomic molecules have one vibration, polyatomic linear molecules have 3V-5 vibrations, and nonlinear molecules have 3V-6 vibrations. Equilibrium stable isotope fractionations are driven mainly by the effects of isotopic substitution on vibrational frequencies.

The two MOs of a diatomic molecule are classified as a, tt, 8, etc., according to whether the projection of angular momentum along the molecular axis is 0, 1, 2, etc. (in units of hUir). Moreover, the antibonding condition is indicated by an asterisk for... 

Judd, B.R., Angular Momentum Theory for Diatomic Molecules, Academic Press, New York, (1975). Monkhorst, H. and Jeziorski, B., J. Chem. Phys. 71, 5268 (1979). 

The molecular orbitals (MOs) are formed by the linear combination of atomic orbitals (LCAO-MO method). For diatomic molecules, the component of the angular momentum (A) in the direction of the bond axis is now important. The energy states are expressed by the symbol... 

The molecular electronic wave functions ipe] are classified using the operators that commute with Hei. For diatomic (and linear polyatomic) molecules, the operator Lz for the component of the total electronic orbital angular momentum along the internuclear axis commutes with Hel (although L2 does not commute with tfel). The Lz eigenvalues are MLh,... 

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