We study the photodissociation of the H+2 molecule by ultrashort Fock-state electromagnetic pulses (EMPs). We use the Born-Oppenheimer treatment combined with an explicit photon number representation via diabatic electrophoton potential surfaces for simplification of the basic equations. We discuss the issue of the number of photon states required and show that six photon states enable good accuracy for photoproduct kinetic energies of up to 3 eV. We calculate photodissociation probabilities and nuclear kinetic-energy (KE) distributions of the photodissociation products for 800 nm, 50-TW/cm2 pulses. We show that KE distributions depend on three pulse durations of 10, 20, and 45 fs and on various initial vibrational states of the molecule. We compare the Fock-state results to those obtained by “conventional,” i.e., coherent-state, laser pulses of equivalent electric fields and durations. The effects of the quantum state of EMPs on the photodissociation dynamics are especially strong for high initial vibrational states of H+2. While coherent-state pulses suppress photodissociation for the high initial vibrational states of H+2, the Fock-state pulses enhance it.

Producing and controlling nonclassical light states are now the subject of intense experimental efforts. In this paper we consider the interaction of such a light state with a small molecule. Specifically, we develop the theory and apply it numerically to calculate in detail how a short pulse of nonclassical light, such as the high intensity Fock state, induces photodissociation in H2+. We compare the kinetic energy distributions and photodissociation yields with the analogous results of quasi-classical light, namely a coherent state. We find that Fock-state light decreases the overall probability of dissociation for low vibrational states of H2+ as well as the location of peaks and line shapes in the kinetic energy distribution of the nuclei.

Molecular electronic ground-state theories, whether ab initio, or semiempirical are most often formulated as a variational principle, where the electronic ground-state energy, considered a linear or nonlinear functional of a reduced density matrix, obtains a constrained minimum. In this communication, we present a Lagrangian analysis of the self-consistent-field electronic structure problem, which does not resort to the concept of orthogonal molecular orbitals. We also develop a method of constrained minimization efficiently applicable to nonlinear energy functional minimization, as well as to linear models such as tight-binding. The method is able to treat large molecules with an effort that scales linearly with the system size. It has built-in robustness and leads directly to the desired minimal solution. Performance is demonstrated on linear alkane and polyene chains.