Relativistic effects potential energy curves

Let us consider how independent /i(i ) 2 effects contribute to the v E) for the hydrogen halides, HX (X = I, Br, and Cl). The curves shown on Fig. 7.6 correspond to relativistic adiabatic potential energy curves (respectively 0 dotted, 0+ dashed, 1 and 2 solid) for HI obtained after diagonalization of the electronic plus spin-orbit Hamiltonians (see Section 3.1.2.2). The strong R-dependence of the electronic transition moment reflects the independence of the relative contributions of the case(a) A-S-Q basis states to each relativistic adiabatic II state. The independent experimental photodissociation cross sections are plotted as solid curves in Fig. 7.7 for HI and HBr. Note that, in addition to the independent variations in the A — S characters of each fl-state caused by All = 0 spin-orbit interactions, all transitions from the X1E+ state to states that dissociate to the X(2P) + H(2S) limit are forbidden in the separated atom limit because they are at best (2Pi/2 <— 2P3/2) parity forbidden electric dipole transitions on the X atom. In the case of the continuum region of an attractive potential, the energy dependence of the dissociation cross section exhibits continuity in the Franck-Condon factor density (see Fig. 7.18 Allison and Dalgarno, 1971 Smith, 1971 Allison and Stwalley, 1973). 

Fig. 4. All-electron, effective potential, and average relativistic effective core potential configuration-interaction potential-energy curves of Xe2 and Xe2+. Dashed curves are from allelectron calculations and AREP curves are less repulsive than EP.

Fig. 6. Average relativistic effective core potential and relativistic effective core potential energy curves for two states of Bi2. HF, Hartree-Fock GVB(pp), eight-configuration perfect-pairing generalized valence bond FVCI, full-valence Cl based on the GVB(pp) wave functions FV7R, full-valence Cl plus single and double promotions to virtual MOs relative to seven-dominant configurations. (The FVCI and FV7R calculations include the REP-based spin-orbit operator.)...

The nature is relativistic. One can not receive the correct potential energy curve without taking into account the relativistic effects. To show the difference between the nonrelativistic and relativistic theory, the results of theoretical calculations for... 

We do not receive a full description of excited states and potential energy curves without the spin-orbit terms. Spin-orbit effect arises due to the interaction of the magnetic dipole of the electronic spin and the movement of electrons in its orbit. For the nonrelativistic case, angular momentum I and spin s are normal constants of motion and they both commute with the nonrelativistic Hamiltonian. For the relativistic case and the Dirac equation neither s nor 1 are normal constants of motion for this case, but the total angular momentum operator j = 1 + sis. 

Edvardsson, D., Lunell, S., and Marian, C.M., Calculation of potential energy curves for Rb2 including relativistic effects. Mol. Phys., 101,2381-2389, 2003. 

W. C. Ermler, Y. S. Lee, K. Pitzer. Ab initio effective core potentials including relativistic effects. IV. Potential energy curves for the ground and several excited states of Au2. j. Chem. Phys., 70 (1979) 293. 

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