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The Journal of Chemical Physics

Temporal coherence in multiphoton absorption. Far off-resonance intermediate states

Peter W. Milonni, Joseph H. Eberly

Published Feb 15, 1978• 62 citations
Publisher

Abstract

We develop a consistent formalism for the treatment of temporal atomic or molecular coherence in multiphoton absorption. The formalism is fully quantum mechanical under the assumption that the exciting laser fields are well described by coherent states. We make use of the language and methodology of resonance physics to the extent possible, but deliberately avoid the rotating-wave approximation, and do not restrict the allowed atomic states to be finite in number or the electric field strengths to be small in magnitude. For compactness in the presentation only electric dipole transitions are considered. As all of the transitions, both stimulated and spontaneous, are due to the activation of quantum mechanical dipoles, it is most efficient to construct the formalism so that it emphasizes the role of dipole operators, and we do this. The one strong restriction imposed here, but avoided in a following paper, is to consider only multiphoton transitions that have one resonance between initial and final states and no intermediate resonance. We describe, in effect, the time dependences associated with the early multiphoton absorption calculations of Bebb and Gold.

DOI
10.1063/1.435928

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We develop a consistent formalism for the treatment of temporal atomic or molecular coherence in multiphoton absorption. The formalism is fully quantum mechanical under the assumption that the exciting laser fields are well described by coherent states. We make use of the language and methodology of resonance physics to the extent possible, but deliberately avoid the rotating-wave approximation, and do not restrict the allowed atomic states to be finite in number or the electric field strengths to be small in magnitude. For compactness in the presentation only electric dipole transitions are considered. As all of the transitions, both stimulated and spontaneous, are due to the activation of quantum mechanical dipoles, it is most efficient to construct the formalism so that it emphasizes the role of dipole operators, and we do this. The one strong restriction imposed here, but avoided in a following paper, is to consider only multiphoton transitions that have one resonance between initial and final states and no intermediate resonance. We describe, in effect, the time dependences associated with the early multiphoton absorption calculations of Bebb and Gold.
The multiple-linear-time-scale method is used to construct a perturbation theory for NNN-level quantum systems subjected to time-dependent perturbations. The secular and small-denominator terms which plague conventional time-dependent perturbation theory are avoided; consequently, the theory is useful for treating long-term behavior and resonant interactions. The introduction of a self-energy operator allows the shifts in energy levels to be displayed explicitly. When the perturbation is the dipole interaction with an electromagnetic field, the successive approximations yield the well-known rotating-wave approximation, corrections due to counter rotating terms, and the Bloch-Siegert frequency shift. The formalism is applicable to arbitrary pulse shapes, provided that $\ensuremath{\parallel}{H}_{1}\ensuremath{\parallel}\ensuremath{\ll}\ensuremath{\hbar}\overline{\ensuremath{\omega}}$, where $\ensuremath{\parallel}{H}_{1}\ensuremath{\parallel}$ represents the inter-action strength and $\overline{\ensuremath{\omega}}$ is a characteristic frequency of the field. Rabi oscillations induced by multiphoton resonances are automatically included, and this effect is demonstrated in the case of a square pulse with frequency approximately one half the resonance frequency for a transition between two vibrational levels of a molecule. These calculations are compared to an exact numerical solution in order to find the limits of validity of the approximation. Even at high intensities ($I\ensuremath{\sim}{10}^{14}$ W/cm2{\mathrm{cm}}^{2}cm2) the shifted resonance frequency is quite accurate; however, the approximate and exact solutions are slightly out of phase, so that the approximate solution can only be trusted for a few Rabi cycles. For much lower intensities ($I\ensuremath{\sim}{10}^{10}$ W/cm2{\mathrm{cm}}^{2}cm2), the approximate solution is valid for many thousands of Rabi cycles.
The multiphoton resonant excitation of three-level atoms in a strong laser field is investigated. The creation of various superposition states is shown. For implementation of these effects either the mean dipole moment in the excited states of an atom or, in three-level systems, a transition dipole moment between excited states (with energies close enough to each other) must be nonzero. The time evolution of the system is found using a nonperturbative resonant approach. Our calculations for the hydrogen atom suggest that by the appropriate optical pulses with moderate strong intensities one can achieve various superposition states by multiphoton resonant excitation.
Attention is focused on the dynamic evolution of the emission spectrum following abrupt excitation of a near-resonant two-level absorber by a strong laser field. The multiphoton character of the absorption-emission process is evident in the AC Stark splitting of the spectrum, which begins approximately half an atomic lifetime after excitation, if the laser field is strong enough. Analytic expressions for the spectra are given of arbitrary laser field strength, atomic lifetime, laser-atom detuning, and the bandwidth of the spectrometer used to analyse the spectrum. Selected graphs are included to illustrate various time-dependent features of the spectrum. The influence on the transient spectrum of three different states of atomic excitation prior to laser irradiation and the effect on the spectrum of irradiation by a phase-noisy laser are also considered. Comparison of the transient spectra from atoms initially prepared in ' pi /2' and '3 pi /2' states show clearly that phase relationships between the irradiating field and the emitting dipole are important even in fluorescence.
A recently proposed collisional time-correlation function method for resonance laser–target interactions in molecular targets is modified and extended to include time-delayed multiphoton processes in the dynamics. The explicitly time-dependent laser and target dynamics in this method is separated into laser electric field and molecular target dipole/susceptibility correlation functions. The first and second order laser field correlation functions, also known as Glauber field correlation functions, are evaluated in a continuum mode description of photon number representation for both resonance and time-delayed multiphoton processes. We show that such a description allows for the incorporation of laser pulse shape and phase coherence in the formalism, while the laser–target interaction dynamics is still described similarly to the resonance single- and multiphoton processes. As an example, the transition rates for a two-photon Gaussian pump–probe dynamics are derived in which we show that the phase coherence between the Gaussian pump and probe pulses can be incorporated and controlled through a single delay-time-dependent parameter.
A five-level model molecule consisting of a ground and four nearly degenerate excited states, where the excited states arise, via static couplings, from the interaction of a doorway state with three background states, is used to investigate neighbouring-level effects and the validity of the generalized rotating-wave or quasi-resonant approximation for such systems. Calculations are performed to determine the (single-photon) absorption spectra associated with the model, and the underlying temporal behaviour of the molecular states, using both RWA and (exact) Floquet techniques, as functions of the frequency and field strength of the applied sinusoidal electric field. For the field strengths studied, corresponding to ground-doorway-state transition coupling strengths (E d - E g) < 0·04, the RWA results for the overall absorption spectra and for the resonance profiles associated with the individual excited states are generally in excellent agreement with exact calculations, although some interesting subtle differences do occur for the largest considered. On the other hand, the temporal development of the molecular states is well represented by the RWA only for small times. The spectral results, as a function of , are used to discuss some of the interesting features, due to neighbouring-level effects involving the nearly degenerate excited states, that occur during the transition from weak to strong molecule-EMF coupled problems. These include intensity stealing by off-resonance molecular states and inversions of the order of resonance frequencies relative to those corresponding to the weak-field limits.