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In this thesis, the interaction of light with matter inside the metallic rectangular waveguide which cover the spontaneous emission and resonance energy transfer are investigated using Green's tensor approach. The preferred approach is to obtain the emission rate and energy transfer rate via Green's tensor. It has been found that the emission rate and energy transfer rate depends upon three factors: the cross-section size of waveguide, position of molecule with respect to the interface, and index-contrast. It is also revealed that in addition of contributions from the propagating modes to emission rate, the energy transfer rate can also be assisted by the evanescent modes in the waveguide, resulting the transfer rate that cannot be completely suppressed as in the spontaneous emission rate.