Amorphous carbon films with sp(3) bonded carbon fractions over 70% are deposited by pulsed laser deposition. However, the optical bandgap obtained from optical transmittance and spectroscopic ellipsometry analysis shows the values to be below 1.0 eV. A wide range of measurements such as electron energy loss spectroscopy, visible Raman, spectroscopic ellipsometry, optical transmittance, and electrical characterization are performed to elucidate the bonding configurations that dictate microstructural, optical and electrical properties, and their linkage to band structure changes. It is found that stress-induced electronic localized states play an important role in the physical properties of the films deposited. The optical bandgap is shown not to be a good measure of the electrical bandgap, especially for high electric field conduction in these tetrahedral amorphous carbon films.