Association of molecules using a resonantly modulated magnetic field

We study the process of associating molecules from atomic gases using a magnetic field modulation that is resonant with the molecular binding energy. We show that maximal conversion is obtained by optimising the amplitude and frequency of the modulation for the particular temperature and density of the gas. For small modulation amplitudes, resonant coupling of an unbound atom pair to a molecule occurs at a modulation frequency corresponding to the sum of the molecular binding energy and the relative kinetic energy of the atom pair. An atom pair with an off-resonant energy has a probability of association which oscillates with a frequency and time-varying amplitude which are primarily dependent on its detuning. Increasing the amplitude of the modulation tends to result in less energetic atom pairs being resonantly coupled to the molecular state, and also alters the dynamics of the transfer from continuum states with off-resonant energies. This leads to maxima and minima in the total conversion from the gas as a function of the modulation amplitude. Increasing the temperature of the gas leads to an increase in the modulation frequency providing the best fit to the thermal distribution, and weakens the resonant frequency dependence of the conversion. Mean-field effects can alter the optimal modulation frequency and lead to the excitation of higher modes. Our simulations predict that resonant association can be effective for binding energies of order $h \times 1$ MHz.Comment: 8 pages latex, figures revised, references updated and typos correcte

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

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

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

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

Reduced dimensionality spin-orbit dynamics of CH3 + HCl reversible arrow CH4 Cl on ab initio surfaces

A reduced dimensionality quantum scattering method is extended to the study of spin-orbit nonadiabatic transitions in the CH3 + HCl reversible arrow CH4 + Cl(P-2(J)) reaction. Three two-dimensional potential energy surfaces are developed by fitting a 29 parameter double-Morse function to CCSD(T)/IB//MP2/cc-pV(T+d)Z-dk ab initio data; interaction between surfaces is described by geometry-dependent spin-orbit coupling functions fit to MCSCF/cc-pV(T+d)Z-dk ab initio data. Spectator modes are treated adiabatically via inclusion of curvilinear projected frequencies. The total scattering wave function is expanded in a vibronic basis set and close-coupled equations are solved via R-matrix propagation. Ground state thermal rate constants for forward and reverse reactions agree well with experiment. Multi-surface reaction probabilities, integral cross sections, and initial-state selected branching ratios all highlight the importance of vibrational energy in mediating nonadiabatic transition. Electronically excited state dynamics are seen to play a small but significant role as consistent with experimental conclusions. (C) 2011 American Institute of Physics. [doi:10.1063/1.3592732