In this paper, we propose a new way of calculating vibrational excited state absorptions by constructing excited states CMESs and using their second-order derivative information to approximate the vibrational transition energies. This is essentially equivalent to performing MD simulations at the zero-temperature limit. We systematically test the new method on a series of 1-D model systems and benchmark against the exact quantum reference. We will show that the results are significantly better than the harmonic approximation results based on the ground state PES. This paper will serve as the theoretical foundation for our future development of using excited states CNEO theory to calculate vibrational excited state absorptions in real molecular systems.