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A model of localized electron wave packets (WPs) with variable position andwidth (floating and breathing) that are spin-coupled as per the valence-bondtheory is presented. It produces accurate potential energy curves of LiH in theground singlet and triplet states. Quantization in a mean-field approximationof the motion of a WP that corresponds to the Li 2s electron generatessemi-quantitative potential energy curves of low energy excited states.Real-time semiquantal dynamics of the WP induced by an intense laser pulsegives high-harmonic generation spectra that capture qualitative features of ahigher-level wave function calculation.

Localized electron wave packet description of chemical bond and excitation: Floating and breathing Gaussian with valence-bond coupling