Numerical Bound State Electron Dynamics of Carbon Dioxide in the Strong-Field Regime

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2010-02, Vol.114 (7), p.2576-2587
• Main Authors: Smith, Stanley M, Romanov, Dmitri A, Li, Xiaosong, Sonk, Jason A, Schlegel, H. Bernhard, Levis, Robert J
• Format: Article
• Language: English
• Subjects: A: Molecular Structure, Quantum Chemistry, General Theory; Carbon Dioxide - chemistry; Computer Simulation; Electrochemistry; Electrons; Time Factors
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp904549d

Time-dependent Hartree−Fock simulations for a linear triatomic molecule (CO2) interacting with a short IR (1.63 eV) three-cycle pulse reveal that the carrier-envelope shape and phase are the essential field parameters determining the bound state electron dynamics during and after the laser−molecule interaction. Analysis of the induced dipole oscillation reveals that the envelope shape (Gaussian or trapezoidal) controls the excited state population distribution. Varying the carrier envelope phase for each of the two pulse envelope shapes considerably changes the excited state populations. Increasing the electric field amplitude alters the relative populations of the excited states, generally exciting higher states. A windowed Fourier transform analysis of the dipole evolution during the laser pulse reveals the dynamics of state excitation and in particular state coupling as the laser intensity increases.