Large scale investments in experimental facilities working in the XUV and X-ray frequency regions have led to a boost in spectroscopic techniques to probe molecular systems. This has also triggered the need to develop quantum-chemical theory and computational tools to interpret and predict such spectral features. Theoretical investigations are capable of relating experimental observations to the structure and dynamics of the molecule. The work presented focuses on theoretical investigations of photoelectron and X-ray photoabsorption spectroscopy of molecules using the coupled cluster framework. Photoelectron spectroscopy requires one to describe the electronic continuum in addition to the bound state wavefunction, thereby leading to further complexities. We present a highly correlated scheme combining Dyson orbital coefficients with multi-centric B-spline time-dependent density functional theory, to compute the photoelectron spectroscopic observables.