Intramolecular coupling effects in optical responses of two-level systems
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Abstract
In this work, the effects of the vibronic coupling on the nonlinear optical properties of organic dyes immersed in a thermal bath with the use of the Four-Wave mixing spectroscopy are evaluated. The isolated molecule is modeled as energy curves of Born-Oppenheimer, consisting of two-electronic states described by harmonic potentials, with minima displaced in energy and nuclear coordinates. Inclusion of a residual Hamiltonian of electronic correlation and/or spin-orbit generates the separation of the two curves according to the rules of avoided crossing. The permanent and transition dipole moments as function of the intramolecular coupling parameters are evaluated. We use the conventional optical Bloch equations, for the calculation of the polarizations induced in the tensorial approach and with them, the nonlinear optical properties. The results show attenuation of the intensity in the optical responses and modifications in their topology, as a consequence of the intramolecular coupling and type of optical transition. Parametric amplifications and the possibility of Switches in the optical properties, arise as a consequence of the insertion of intramolecular couplings.
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