Ab Initio MD Simulation of Laser-Matter Interactions is a Hot Area in the Study of the Mechanisms of Photo-Dissociation, Photo-Ionization and Laser Induced Chemical Reactions. the Major Problems in the Study of Laser-Molecule Interactions Are to Determine the Energies and Wave Functions of Molecular Vibration States and the Molecular Transition Dipole Moments. an Efficient Method is Presented to Calculate the Intramolecular Potential Energies and Electrical Dipole Moments of CO2 Molecules at the Electronic Ground State by Solving the Kohn-Sham (KS) Equation for a Total of 101,992 Nuclear Configurations. the Projector-Augmented Wave (PAW) Exchange-Correlation Potential Functionals and Plane Wave (PW) Basis Functions Were Used in Solving the KS Equation. the Calculated Intra-Molecular Potential Function Was Then Included in the Pure Vibrational Schrödinger Equation to Determine the Vibrational Energy Eigen Values and Eigen Functions. the Vibrational Wave Functions Combined with the Calculated Dipole Moment Function Were Used to Determine the Transition Dipole Moments. the Calculated Results Have a Good Agreement with Experimental Values. These Results Can Be Further Used to Determinations of Molecular Spectroscopy and Laser Absorption Coefficients. Copyright © 2008 by ASME.