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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 6714-6727 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We investigate the properties of a homogeneously broadened three-level system interacting with two optical fields, Eω1(x,t) and Eω2(x,t), with central frequencies ω1 and ω2 whose amplitudes are assumed to be slowly varying in time compared with dephasing times of the optical transitions. We calculate Raman susceptibilities allowing each transition to be induced by both fields and without employing the rotating wave approximation (RWA); this enables correct calculation of the optical response of the medium when the fields are on-resonance or arbitrarily far off-resonance with the Raman transition. In some frequency regions the RWA causes substantial errors. A distinction is drawn between two different types of RWA: (a) a neglect of off-resonant components of the polarization for direct optical transitions, and (b) neglect of off-resonant components of off-diagonal density matrix elements of order Eω1(x,t)Eω2(x,t)* in the field amplitudes. The first RWA is known to become inaccurate when the pump frequency is significantly off-resonance with the pump transition. We show that the second RWA becomes inaccurate when ||ω1−ω2|| is small or comparable to the active Raman mode frequency (even when the field are close to resonance). Calculations based upon our expressions show that when the pump frequency is close to resonance with the optical transition from the ground state, a nonlinear absorption at the Stokes shifted frequency occurs. This absorption can significantly decrease the Raman gain. Also, we find that Rabi splittings in a three-level system can occur even when the pulse durations of the incident fields are short compared with the T1 times of the system. We solve analytically for the optical response of the system to two fields of arbitrary strength and frequency. We analyze this solution and its perturbative expansion in the field amplitudes. We use the Maxwell–Bloch equations developed here to propagate time-dependent pulses.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 7528-7530 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We demonstrate that stimulated Raman adiabatic passage (STIRAP) of population from a ground state to an excited state of an atom or molecule is not an optimal control solution to the problem of maximizing the population in the excited state.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 8869-8876 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We derive an algorithm to calculate quantum transmission and reflection amplitudes (S-matrix elements) for rearrangement reactions using the invariant imbedding method. Our approach can incorporate closed channels, treat complex potentials (to simulate decay), and can be used within an adiabatic representation (in which derivative coupling terms are present) or within a diabatic representation. The method can also be used to determine bound-state energies when only closed channels are present. The method is demonstrated on a rearrangement problem with two coupled potential surfaces (four channels) as a function of energy in the energy region from the lowest channel threshold through the highest channel threshold.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 5808-5823 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Nonadiabatic matrix elements, when computed using a Born-Oppenheimer (BO) basis, do not vanish asymptotically because the motion of the electrons with the nuclei at large internuclear separations is not taken into account. We apply a method suggested by Delos [Rev. Mod. Phys. 53, 287 (1981)] to include the effect of electron translation factors in a quantum-mechanical framework, thus correcting the BO basis to incorporate proper boundary conditions. We calculate the nonadiabatic matrix elements for H2+ and its isotopic variants. We focus our calculations on HD+, for which experimental results exist, and calculate its vibronic spectrum. This is the first application of this method to calculate high precision spectroscopic information for molecular systems. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 5291-5298 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We compare the results of full density matrix calculations with recently reported experimental results describing the population transfer in Na2 using Raman scattering with the fundamental laser beam temporally shifted relative to the Stokes laser beam. Our calculations confirm the conclusion that almost total transfer of the population into the terminal level of the Raman transition can be achieved when the laser frequencies are tuned to resonance and the fundamental laser beam is temporally delayed relative to the Stokes shifted laser beam but still partially overlapping it. We analyze our results when the frequencies of the lasers are tuned off-resonance as a function of the Rabi frequencies and the detuning, and compare with experimental and theoretical results. The alignment of the terminal level as a function of time displacement of the Stokes and pump beams is predicted.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 9079-9084 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Application of a discrete variable representation (DVR) to Hamiltonians derived in a nonadiabatic basis or Hamiltonians obtained by making a nonlinear dependent-coordinate transformation, leads to a Hamiltonian matrix which (a) cannot be evaluated without explicitly performing summations, or (b) is not Hermitian. We develop a prescription to avoid these difficulties. Specific examples involving Fourier grid Hamiltonian DVRs are presented. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 8463-8466 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We develop a method of quantum state imaging (determination of the full initial density matrix of an atomic or molecular state) using time dependent spectrum data. The method determines the wave function (or more generally, the density matrix) created via an arbitrary excitation process even when degenerate rotational degrees of freedom are present. It requires application of external electric and magnetic fields, without which determination of the full density matrix is in general impossible. In the presence of external fields, quantum state imaging from angle and polarization resolved (or unresolved) time dependent spectrum data is feasible. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 9704-9708 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We derive and demonstrate an invariant imbedding method for calculating the S matrix for scattering problems involving a first derivative term in the Schrödinger equation for the relative motion. This method can be used directly on scattering problems derived using molecular structure calculations that determine adiabatic potential energies and their derivative coupling matrix elements. A critical discussion of the procedures that transform from an adiabatic to a diabatic representation is presented.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 3339-3341 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Some simple schemes for obtaining complete alignment and orientation of atoms and molecules using stimulated Raman scattering with temporally shifted laser fields is proposed. (AIP)
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 5681-5685 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present results of density matrix calculations describing population transfer in a four level system via stimulated Raman scattering with three laser pulses whose frequencies are in (or nearly in) resonance with the transitions between the levels. A high degree of transfer to the terminal level is possible via transitions through the two intermediate excited levels, despite the large decay rates of both levels compared with the inverse of the laser pulse durations, provided that the pulse timing sequences are correctly adjusted. Hence multiple stimulated Raman scattering can be an efficient method of moving population into a given molecular level.
    Type of Medium: Electronic Resource
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