Electronic-rotational interactions

In linear molecules, the electronic-rotation interaction terms in H cause the A-type doubling of electronic states, whereas the vibration-rotation interaction terms in H cause the /-type doubling of vibrational states. In addition, the perturbation H can cause interactions between vibration-rotation levels of different electronic states. If it happens that two vibration rotation levels of different electronic states of a molecule have... 

INTRAMOLECULAR ELECTRONIC-ROTATIONAL INTERACTIONS, MAGNETIC FIELD DEPENDENT INTERACTIONS, AND THE MOLECULAR ZEEMAN EFFECT... 

M. Schwarz, R. Duchowicz, W. Demtroder, C. Jungen, Autoionizing Rydbeig states of Li2 analysis of electronic-rotational interactions. J. Chem. Phys. 89, 5460 (1988)... 

The terms of eqs. (19) and (20) containing the rotation angle 8 are responsible for electron—rotation interaction. For simplicity we give in eq. (20) only those second-order terms in u which take into account the rotation about one of the crystallographic axes. 

The tensor of elastic compliancy S T) = C T), and die elastic constant matrix (ignoring the terms due to electron-rotation interaction) is equal to ... 

The free energy of a crystal in a magnetically ordered phase or in an applied magnetic field may be presented only as an expansion in powers of displacement tensor components Uafi (see eqs. 92 and 96) the contributions of finite deformations and electron-rotation interactions to isothermal elastic constants. ... 

The final form of the Born-Handy formula consists of three terms The first one represents the electron-vibrational interaction. I will not present the numerical details for H2, HD and D2 molecules here, it can be found in our previous work. The most important result here is that the electron-vibrational Hamiltonian is totally inadequate for the description of the adiabatic correction to the molecular groundstates its contribution differs almost in one decimal place from the real values acquired from the Born-Handy formula. In the case of concrete examples -H2, HD and D2 molecules - the first term contributes only with ca 20% of the total value. The dominant rest - 80% of the total contribution - depends of the electron-translational and electron-rotational interaction [22]. This interesting effect occurs on the one-particle level, and it justifies the use of one-determinant expansion of the wave function (28.2). Of course, we can calculate the corrections beyond the Hartree-Fock approximation by means of many-body perturbation theory, as it was done in our work [22], but at this moment it is irrelevant to further considerations. 

By obtaining values for B in various vibrational states within the ground electronic state (usually from an emission spectrum) or an excited electronic state (usually from an absorption spectrum) the vibration-rotation interaction constant a and, more importantly, B may be obtained, from Equation (7.92), for that electronic state. From B the value of for that state easily follows. 

OIDEP usually results from Tq-S mixing in radical pairs, although T i-S mixing has also been considered (Atkins et al., 1971, 1973). The time development of electron-spin state populations is a function of the electron Zeeman interaction, the electron-nuclear hyperfine interaction, the electron-electron exchange interaction, together with spin-rotational and orientation dependent terms (Pedersen and Freed, 1972). Electron spin lattice relaxation Ti = 10 to 10 sec) is normally slower than the polarizing process. 

In Equation (15), R others encompasses all secondary interactions which are not included in the first two terms (for instance the interaction with an unpaired electron, the spin-rotation interaction,...). By contrast, the expression of the cross-relaxation rate is simply... 

In a previous study of cyclic SiCs, a residual inertial defect of only slightly smaller magnitude was found, despite the fact that an extremely high level of calculation (surpassing that in the present study) was used to determine the vibration-rotation interaction contributions to the rotational constants. This was subsequently traced to the so-called electronic contribution, which arises from a breakdown of the assumption that the atoms can be treated as point masses at the nuclear positions. Corrections for this somewhat exotic effect were carried out in that work and reduced the inertial defect from about 0.20 to less than 0.003 amu A. However, the associated change in the rotational constants had an entirely negligible effect on the inferred structural parameters. Hence, this issue is not considered further in this work. 

The basic idea of the slow-motion theory is to treat the electron spin as a part of the lattice and limit the spin part of the problem to the nuclear spin rather than the IS system. The difficult part of the problem is to treat, in an appropriate way, the combined lattice, now containing the classical degrees of freedom (such as rotation in condensed matter) as well as quantized degrees of freedom (such as the electron Zeeman interaction). The Liouville superoperator formalism is very well suited for treating this type of problems. 

The simplest possible physical picture of the lattice contains the electron Zeeman interaction, the axially symmetric ZFS (whose principal axis coincides with the dipole-dipole axis) and the molecular rotation. The corresponding Liouvillian is given by ... 

When the temperature of a molecule is increased, rotational and vibrational modes are excited and the internal energy is increased. The excitation of each degree of freedom as a function of temperature can be calculated by way of statis-hcal mechanics. Though the translational and rotational modes of a molecule are fully excited at low temperatures, the vibrational modes only become excited above room temperature. The excitation of electrons and interaction modes usually only occurs at well above combushon temperatures. Nevertheless, dissocia-hon and ionization of molecules can occur when the combustion temperature is very high. 

A AH < kT has important consequences. As the temperature is lowered to where AHg, kT, strong electron-phonon interactions must manifest themselves. Direct evidence for mode softening and strong electron-phonon coupling in the internal Ty < T < 250 K has been provided by measurements of the Mdssbauer recoiless fraction and the X-ray Debye-Waller factor as well as of muon-spin rotation Therefore, it would be... 

The first line in this expression describes the rotational structure with color spin-doubling and the hyperflne interaction of the effective electron spin S with the nuclear spin I. B is the rotational constant, J is the electron-rotational angular momentum, A is the o -doubling constant. The second line describes the interaction of the molecule with the external fields B and E, (A is the unit vector directed from the heavy nucleus to the light one). The last line corresponds to the P-odd electromagnetic interaction of the electrons with the anapole moment of the nucleus described by the constant /ca [40], P,T-odd interaction of the electron EDM de with the interamolecular field, and P,T-odd scalar interactions of the electrons with the heavy nucleus [90]. 

The rotational relaxation times of these nitrocompounds have not been measured. Comparison with the studies of perylene by Klein and Haar [253] suggests that most of these nitrocompounds have rotational times 10—20 ps in cyclohexane. For rotational effects to modify chemical reaction rates, significant reaction must occur during 10ps. This requires that electron oxidant separations should be <(6 x 10-7x 10-11)J/2 2 nm. Admittedly, with the electron—dipole interaction, both the rotational relaxation and translational diffusion will be enhanced, but to approximately comparable degrees. If electrons and oxidant have to be separated by < 2 nm, this requires a concentration of > 0.1 mol dm-3 of the nitrocompound. With rate coefficients 5 x 1012 dm3 mol-1 s 1, this implies solvated electron decay times of a few picoseconds. Certainly, rotational effects could be important on chemical reaction rates, but extremely fast resolution would be required and only mode-locked lasers currently provide < 10 ps resolution. Alternatively, careful selection of a much more viscous solvent could enable reactions to show both translational and rotational diffusion sufficiently to allow the use of more conventional techniques. 

Whereas for diatomic molecules the vibration-rotation interaction added only a small correction to the energy, for a number of polyatomic molecules the vibration-rotation interaction leads to relatively large corrections. Similarly, although the Born-Oppenheimer separation of electronic and nuclear motions holds extremely well for diatomic molecules, it occasionally breaks down for polyatomic molecules, leading to substantial interactions between electronic and nuclear motions. 

Finally, spin-orbit interaction has often been considered as the cause of states of mixed permutational symmetry. There are, however, a variety of other spin interactions which may accomplish such mixing electron spin-electron spin, electron spin-nuclear spin, spin-other-orbit, and spin rotation interactions. That other such spin interactions may enhance spin-forbidden processes in organic molecules is frequently ignored, though they may be of importance.66,136... 

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