A rotating-wave approximation (RWA) is developed to describe the evolution of a two-level system, which has permanent dipole moments, interacting with a pulsed laser. Comparisons with exact calculations for one- and two-photon excitations involving the two lowest vibrational states of the ground electronic state of ${\mathrm{HeH}}^{+}$ are given to illustrate the validity of the RWA formula.
A rotating-wave approximation (RWA) is developed to describe the evolution of a two-level system, which has permanent dipole moments, interacting with a pulsed laser. Comparisons with exact calculations for one- and two-photon excitations involving the two lowest vibrational states of the ground electronic state of HeH+ are given to illustrate the validity of the RWA formula.
A rotating-wave approximation (RWA) is developed to describe the interaction of a two-level system, which has permanent dipole moments, with two pulsed lasers. The RWA expressions for the time-dependent populations of the molecular states are applied to model laser-molecule interactions and tested by comparison with exact results. The results are used to discuss the pulsed-laser phase control of molecular excitation through the interplay of competing one- and two-photon resonances involving the effects of a nonzero difference d between the permanent dipoles of the two states involved in the transition; the competition vanishes if d=0.
The interaction of two continuous wave electric fields (lasers) with a two-level molecule, that has a nonzero difference d, between the permanent dipoles of the two states involved in a multiphoton two-color transition, is studied in the rotating wave approximation and by using exact methods. Analytical rotating wave approximation results for the time-dependent populations of the molecular states and for the resonance profiles are derived and used to help discuss the effects of permanent dipole moments in the two-color absorption problem. Several examples of multiphoton, two-color, two-level resonance profiles calculated in the rotating wave approximation and by using exact techniques, are employed for illustrative purposes. They are used to help quantify the conditions for the validity of the two-color rotating wave approximation, which are considerably more restrictive than the analogous conditions for the one-color rotating wave approximation with d≠0, and to illustrate the interpretive and predictive nature of the rotating wave approximation results. For example, there are many multiphoton, two-color transitions that are available if a molecule possesses permanent dipoles (d≠0). The analytic rotating wave approximation expression for the molecule-two laser coupling can often be used to reliably estimate the field parameters of the two lasers that are required to optimize a given transition relative to others.
The spectral and dynamic effects associated with a non-zero difference, d, between the permanent dipole moments of two molecular states involved in a transition, are investigated for a variety of electromagnetic field-molecule interactions. Both analytical and exact numerical techniques are used to solve the time-dependent Schrodinger equation and to obtain the temporal populations of the molecular states and the associated absorption spectra, for molecular interactions with a Gaussian pulsed, or one or two continuous wave (CW), laser(s).;Analytical rotating wave approximation results are derived for a single CW laser interacting with a two-level d {dollar}\\ne{dollar} 0 molecule with an excited state lifetime, and for a two-level d {dollar}\\ne{dollar} 0 molecule interacting with two CW lasers. A symmetry-adapted Riemann product integral method for exact calculations of pulsed laser-molecule interactions is developed and applied to specific problems. The Floquet technique for the treatment of periodic Hamiltonians is extended to accommodate the interaction of a molecule with two CW lasers.;The one-field RWA results are used to predict and interpret the effects of permanent dipoles on the temporal behaviour of the molecular states for a decaying two-level system interacting with a CW laser, and for a non-decaying two-level system interacting with a pulsed laser. It is shown that the excited state lifetime and the pulse duration can act as internal and external probes, respectively, of the temporal effects of permanent dipoles, relative to the often-studied d = 0 problem. The two-field analytical RWA solutions are used to help discuss and predict the effects of permanent dipole moments in two-laser multi-photon transitions. Several examples of multi-photon, two-colour, two-level resonance profiles, calculated in the RWA and by using exact Floquet techniques, are used to demonstrate how particular multi-photon transitions can be optimized, and to help quantify the conditions for the validity of the two-colour RWA. The effects of neighbouring energy levels on the transition of interest, for both probe and pump-probe laser-molecule interactions, are investigated using a series of three- to seven-level model molecular systems.
A rotating-wave approximation (RWA) for the single-photon and multiphoton resonance profiles for a two-level molecule interacting with both sinusoidal and static electric fields is derived. Included is a useful expression for the coupling between the molecule and the applied sinusoidal field which exhibits the effects of both diagonal dipole matrix elements (permanent dipole moments) and the applied static electric field. Comparisons of the RWA results with exact two-level calculations provide qualitative information concerning the validity of the RWA as a function of molecular and field parameters. These examples are also used to illustrate the interpretive nature of the RWA results for the resonance profiles and some of the effects of permanent dipoles and static fields on the profiles. Of particular interest are examples involving Boltzmann rotationally averaged spectra as a function of temperature where it is shown that minima in the spectra occurring for high temperatures can be reduced or removed completely if the temperature or applied static field is reduced.
One of the purposes of this paper is to develop an analytical many-level generalized rotating wave approximation (GRWA), including the effects of permanent dipoles, for the excitation of many-level molecules through the simultaneous absorption of two photons. Included are expressions for the two-photon laser–molecule coupling C, and its two components Cd and Cv corresponding to the direct permanent dipole and the virtual state excitation mechanisms, respectively, and related observables such as the time-dependent populations of the initial and final states of the excitation process and resonance profiles. This GRWA treatment also includes an energy shift parameter e, which causes shifts in the position of the resonance energy as the laser intensity increases. The effects of permanent dipoles are very different in Cv and e versus Cd. These effects have been discussed previously for Cd using analytic two-level RWA approaches. The analytical results for Cv and e obtained here are new as is their use in discussing the influence of permanent dipoles in the parts of the two-photon excitation process involving virtual states. In the absence of permanent dipoles Cd is zero whereas Cv and e are not; they equal the corresponding perturbation theory results. The GRWA and perturbative results are related by Bessel function damping functions which, for dipolar molecules, damp out the divergence of the perturbative results as the laser intensity increases. Illustrative examples are given for a two-photon excitation involving a model chromophore which has a significant virtual state contribution through both the laser–molecule coupling and the energy shift parameter.
Perturbative corrections are derived for the rotating-wave approximation (RWA) for the single-photon and multiphoton resonance profiles due to the interaction between a two-level molecule, with nonzero permanent dipoles, and a sinusoidal time-dependent electric field. The derivation is carried out through the use of a Floquet secular equation that introduces the effects of the permanent dipole moments into the problem through the argument, d\ensuremath{\cdot}e^scrE/\ensuremath{\omega}, of Bessel functions contained in molecule-laser coupling parameters; here d=${\ensuremath{\mu}}_{22}$-${\ensuremath{\mu}}_{11}$, where ${\ensuremath{\mu}}_{\mathrm{ii}}$ is the permanent dipole of molecular state i, and scrE, e^, and \ensuremath{\omega} are the field strength, direction of polarization unit vector, and the circular frequency of the electromagnetic field (EMF). Expansions for the N-photon resonance profiles and the associated resonance frequencies and full widths at half maximum, in powers of the couplings between the transition and permanent dipole moments and the applied EMF, are obtained by expanding the Bessel functions in the perturbative results and are compared with those in the literature (available mostly for d=0 only). The perturbative results, and a series of exactly calculated two-level model absorption spectra, are used to discuss (1) the ability of the explicit perturbative corrections to the RWA to explain the differences between exact and RWA resonance profiles (for example, the positive or negative Bloch-Siegert shifts and dynamic backgrounds absent in the RWA), (2) the usefulness of the perturbative corrections in general, and (3) the effects of permanent dipoles on single-photon and multiphoton absorption spectra.