The theory of the 14N hyperfine interaction in the B 2 E+ state of CN has been considered by Radford [8] the effective Hamiltonian is the same as that used in chapter 10 for the ground state of CN. Using Frosch and Foley constants [9] it is written, in cartesian form, [Pg.875]

The matrix elements of (11.2) in a case (b) representation for CN in its ground state were derived in chapter 10 Radford [8] obtained the following values of the constants (in MHz) [Pg.875]

As we have shown in Appendix 8.5, and elsewhere, to is the axial component of the dipolar interaction obtained from the fourth term in equation (11.2). The large value of the Fermi contact constant is consistent with a model in which the unpaired electron occupies a a-type molecular orbital which has 45% N atom, v character. Radford produced convincing arguments to show that the model is also consistent with the small dipolar hyperfine constant, and also the electric quadrupole coupling constant. [Pg.875]

This pioneering study of the CN radical was not a true double resonance experiment because it did not need a separate radiation source to produce the initial electronic excitation. Nevertheless it has many of the other elements common to double resonance, as we shall see, and was a landmark study in the field. [Pg.875]

Volumetric flow rate Number of sites Heating rate Inlet pressure of reactant A Inlet pressure of reactant B Total pressure Steady-state reaction temperamre 30 cc min 2x 10 0.333 K s 5-100 Torr 10 Torr 760 Torr 275 - 375 K [Pg.345]

The four sensitivity equations (Equations 6.56a-d) should be solved simultaneously with the two state equations (Equation 6.52). Integration of these six [=nx(p+l)=2x(2+l)] equations yields x(t) and G(t) which are used in setting up matrix A and vector b at each iteration of the Gauss-Newton method. [Pg.123]

This line should cross the y axis at a value of b because when x is 0, y must be 0 + b. The slope of the graph is given by the multiplier a. For example, when the equation states that y = 2x, then y will be 4 when x is 2, and 8 when x is 4, etc. The slope of the line will, therefore, be twice as steep as that of the line given by y = lx. [Pg.5]

First, the successive excitation pathway is discussed. In Fig. 27 we show the two control fields that act after each other (lower panel). Scaling parameters of = 5 x 10-3 a.u. and =2x 10-3 a.u. are employed. As in the case of the Na2 population transfer (Section VII), the field E (t) consists of a pulse sequence (lower panel), which leads to a stepwise increase of the excited-state population. The field is switched off at 5 ps, and the heating field E2(t) starts to interact with the system. Oscillations characterized by the excited-state vibrational period are seen. A fast dissociation (seen in the increase of B (t), upper panel of Fig. 27) is triggered, but also a population transfer between the two electronic states and predissociation takes place. For the present pulse parameters we find a total dissociation yield B (t —> oo) of about 30%. [Pg.70]

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