Sewing sound quantum flesh onto classical bones

Semiclassical transformation theory implies an integral representation for stationary-state wave functions $\psi_m(q)$ in terms of angle-action variables ($\theta,J$). It is a particular solution of Schr\"{o}dinger's time-independent equation when terms of order $\hbar^2$ and higher are omitted, but the pre-exponential factor $A(q,\theta)$ in the integrand of this integral representation does not possess the correct dependence on $q$. The origin of the problem is identified: the standard unitarity condition invoked in semiclassical transformation theory does not fix adequately in $A(q,\theta)$ a factor which is a function of the action $J$ written in terms of $q$ and $\theta$. A prescription for an improved choice of this factor, based on succesfully reproducing the leading behaviour of wave functions in the vicinity of potential minima, is outlined. Exact evaluation of the modified integral representation via the Residue Theorem is possible. It yields wave functions which are not, in general, orthogonal. However, closed-form results obtained after Gram-Schmidt orthogonalization bear a striking resemblance to the exact analytical expressions for the stationary-state wave functions of the various potential models considered (namely, a P\"{o}schl-Teller oscillator and the Morse oscillator).Comment: RevTeX4, 6 page

Measuring nonadiabaticity of molecular quantum dynamics with quantum fidelity and with its efficient semiclassical approximation

We propose to measure nonadiabaticity of molecular quantum dynamics rigorously with the quantum fidelity between the Born-Oppenheimer and fully nonadiabatic dynamics. It is shown that this measure of nonadiabaticity applies in situations where other criteria, such as the energy gap criterion or the extent of population transfer, fail. We further propose to estimate this quantum fidelity efficiently with a generalization of the dephasing representation to multiple surfaces. Two variants of the multiple-surface dephasing representation (MSDR) are introduced, in which the nuclei are propagated either with the fewest-switches surface hopping (FSSH) or with the locally mean field dynamics (LMFD). The LMFD can be interpreted as the Ehrenfest dynamics of an ensemble of nuclear trajectories, and has been used previously in the nonadiabatic semiclassical initial value representation. In addition to propagating an ensemble of classical trajectories, the MSDR requires evaluating nonadiabatic couplings and solving the Schr\"{o}dinger (or more generally, the quantum Liouville-von Neumann) equation for a single discrete degree of freedom. The MSDR can be also used to measure the importance of other terms present in the molecular Hamiltonian, such as diabatic couplings, spin-orbit couplings, or couplings to external fields, and to evaluate the accuracy of quantum dynamics with an approximate nonadiabatic Hamiltonian. The method is tested on three model problems introduced by Tully, on a two-surface model of dissociation of NaI, and a three-surface model including spin-orbit interactions. An example is presented that demonstrates the importance of often-neglected second-order nonadiabatic couplings.Comment: 14 pages, 4 figures, submitted to J. Chem. Phy

The method of Gaussian weighted trajectories. V. On the 1GB procedure for polyatomic processes

In recent years, many chemical reactions have been studied by means of the quasi-classical trajectory (QCT) method within the Gaussian binning (GB) procedure. The latter consists in "quantizing" the final vibrational actions in Bohr spirit by putting strong emphasis on the trajectories reaching the products with vibrational actions close to integer values. A major drawback of this procedure is that if N is the number of product vibrational modes, the amount of trajectories necessary to converge the calculations is ~ 10^N larger than with the standard QCT method. Applying it to polyatomic processes is thus problematic. In a recent paper, however, Czako and Bowman propose to quantize the total vibrational energy instead of the vibrational actions [G. Czako and J. M. Bowman, J. Chem. Phys., 131, 244302 (2009)], a procedure called 1GB here. The calculations are then only ~ 10 times more time-consuming than with the standard QCT method, allowing thereby for considerable numerical saving. In this paper, we propose some theoretical arguments supporting the 1GB procedure and check its validity on model test cases as well as the prototype four-atom reaction OH+D_2 -> HOD+D

Coherent Control and Entanglement in the Attosecond Electron Recollision Dissociation of D2+

We examine the attosecond electron recollision dissociation of D2+ recently demonstrated experimentally [H. Niikura et al., Nature (London) 421, 826 (2003)] from a coherent control perspective. In this process, a strong laser field incident on D2 ionizes an electron, accelerates the electron in the laser field to eV energies, and then drives the electron to recollide with the parent ion, causing D2+ dissociation. A number of results are demonstrated. First, a full dimensional Strong Field Approximation (SFA) model is constructed and shown to be in agreement with the original experiment. This is then used to rigorously demonstrate that the experiment is an example of coherent pump-dump control. Second, extensions to bichromatic coherent control are proposed by considering dissociative recollision of molecules prepared in a coherent superposition of vibrational states. Third, by comparing the results to similar scenarios involving field-free attosecond scattering of independently prepared D2+ and electron wave packets, recollision dissociation is shown to provide an example of wave-packet coherent control of reactive scattering. Fourth, this analysis makes clear that it is the temporal correlations between the continuum electron and D2+ wave packet, and not entanglement, that are crucial for the sub-femtosecond probing resolution demonstrated in the experiment. This result clarifies some misconceptions regarding the importance of entanglement in the recollision probing of D2+. Finally, signatures of entanglement between the recollision electron and the atomic fragments, detectable via coincidence measurements, are identified

Statistical Mechanics for Unstable States in Gel'fand Triplets and Investigations of Parabolic Potential Barriers

Free energies and other thermodynamical quantities are investigated in canonical and grand canonical ensembles of statistical mechanics involving unstable states which are described by the generalized eigenstates with complex energy eigenvalues in the conjugate space of Gel'fand triplet. The theory is applied to the systems containing parabolic potential barriers (PPB's). The entropy and energy productions from PPB systems are studied. An equilibrium for a chemical process described by reactions $A+CB\rightleftarrows AC+B$ is also discussed.Comment: 14 pages, AmS-LaTeX, no figur

Pulse-driven near-resonant quantum adiabatic dynamics: lifting of quasi-degeneracy

We study the quantum dynamics of a two-level system driven by a pulse that starts near-resonant for small amplitudes, yielding nonadiabatic evolution, and induces an adiabatic evolution for larger amplitudes. This problem is analyzed in terms of lifting of degeneracy for rising amplitudes. It is solved exactly for the case of linear and exponential rising. Approximate solutions are given in the case of power law rising. This allows us to determine approximative formulas for the lineshape of resonant excitation by various forms of pulses such as truncated trig-pulses. We also analyze and explain the various superpositions of states that can be obtained by the Half Stark Chirped Rapid Adiabatic Passage (Half-SCRAP) process.Comment: 21 pages, 12 figure

Strong-field dipole resonance. I. Limiting analytical cases

We investigate population dynamics in N-level systems driven beyond the linear regime by a strong external field, which couples to the system through an operator with nonzero diagonal elements. As concrete example we consider the case of dipolar molecular systems. We identify limiting cases of the Hamiltonian leading to wavefunctions that can be written in terms of ordinary exponentials, and focus on the limits of slowly and rapidly varying fields of arbitrary strength. For rapidly varying fields we prove for arbitrary $N$ that the population dynamics is independent of the sign of the projection of the field onto the dipole coupling. In the opposite limit of slowly varying fields the population of the target level is optimized by a dipole resonance condition. As a result population transfer is maximized for one sign of the field and suppressed for the other one, so that a switch based on flopping the field polarization can be devised. For significant sign dependence the resonance linewidth with respect to the field strength is small. In the intermediate regime of moderate field variation, the integral of lowest order in the coupling can be rewritten as a sum of terms resembling the two limiting cases, plus correction terms for N>2, so that a less pronounced sign-dependence still exists.Comment: 34 pages, 1 figur

From angle-action to Cartesian coordinates: A key transformation for molecular dynamics

The transformation from angle-action variables to Cartesian coordinates is a crucial step of the (semi) classical description of bimolecular collisions and photo-fragmentations. The basic reason is that dynamical conditions corresponding to experiments are ideally generated in angle-action variables whereas the classical equations of motion are ideally solved in Cartesian coordinates by standard numerical approaches. To our knowledge, the previous transformation is available in the literature only for triatomic systems. The goal of the present work is to derive it for polyatomic ones.Comment: 10 pages, 11 figures, submitted to J. Chem. Phy

The quality of different types of child care at 10 and 18 months. A comparison between types and factors related to quality.

The quality of care offered in four different types of non-parental child care to 307 infants at 10 months old and 331 infants at 18 months old was compared and factors associated with higher quality were identified. Observed quality was lowest in nurseries at each age point, except that at 18 months they offered more learning activities. There were few differences in the observed quality of care by child-minders, grandparents and nannies, although grandparents had somewhat lower safety and health scores and offered children fewer activities. Cost was largely unrelated to quality of care except in child-minding, where higher cost was associated with higher quality. Observed ratios of children to adults had a significant impact on quality of nursery care; the more infants or toddlers each adult had to care for, the lower the quality of the care she gave them. Mothers' overall satisfaction with their child's care was positively associated with its quality for home-based care but not for nursery settings