Long-range interactions between an atom in its ground S state and an open-shell linear molecule

Theory of long-range interactions between an atom in its ground S state and a linear molecule in a degenerate state with a non-zero projection of the electronic orbital angular momentum is presented. It is shown how the long-range coefficients can be related to the first and second-order molecular properties. The expressions for the long-range coefficients are written in terms of all components of the static and dynamic multipole polarizability tensor, including the nonadiagonal terms connecting states with the opposite projection of the electronic orbital angular momentum. It is also shown that for the interactions of molecules in excited states that are connected to the ground state by multipolar transition moments additional terms in the long-range induction energy appear. All these theoretical developments are illustrated with the numerical results for systems of interest for the sympathetic cooling experiments: interactions of the ground state Rb($^2$S) atom with CO($^3\Pi$), OH($^2\Pi$), NH($^1\Delta$), and CH($^2\Pi$) and of the ground state Li($^2$S) atom with CH($^2\Pi$).Comment: 30 pages, 3 figure

Overlapping Resonances Interference-induced Transparency: The S0→S2/S1S_0 \to S_2/S_1 Photoexcitation Spectrum of Pyrazine

The phenomenon of "overlapping resonances interference-induced transparency" (ORIT) is introduced and studied in detail for the $S_0 \to S_2/S_1$ photoexcitation of cold pyrazine (C$_4$H$_4$N$_2$). In ORIT a molecule becomes transparent at specific wavelengths due to interferences between envelopes of spectral lines displaying overlapping resonances. An example is the $S_2\leftrightarrow S_1$ internal conversion in pyrazine where destructive interference between overlapping resonances causes the $S_0 \to S_2/S_1$ light absorption to disappear at certain wavelengths. ORIT may be of practical importance in multi-component mixtures where it would allow for the selective excitation of some molecules in preference to others. Interference induced cross section enhancement is also shown.Comment: 13 pages, 7 figure

How to Measure the Quantum State of Collective Atomic Spin Excitation

The spin state of an atomic ensemble can be viewed as two bosonic modes, i.e., a quantum signal mode and a $c$-numbered ``local oscillator'' mode when large numbers of spin-1/2 atoms are spin-polarized along a certain axis and collectively manipulated within the vicinity of the axis. We present a concrete procedure which determines the spin-excitation-number distribution, i.e., the diagonal elements of the density matrix in the Dicke basis for the collective spin state. By seeing the collective spin state as a statistical mixture of the inherently-entangled Dicke states, the physical picture of its multi-particle entanglement is made clear.Comment: 6 pages, to appear in Phys. Rev.

Cosmic microwave background constraints on cosmological models with large-scale isotropy breaking

Several anomalies appear to be present in the large-angle cosmic microwave background (CMB) anisotropy maps of WMAP, including the alignment of large-scale multipoles. Models in which isotropy is spontaneously broken (e.g., by a scalar field) have been proposed as explanations for these anomalies, as have models in which a preferred direction is imposed during inflation. We examine models inspired by these, in which isotropy is broken by a multiplicative factor with dipole and/or quadrupole terms. We evaluate the evidence provided by the multipole alignment using a Bayesian framework, finding that the evidence in favor of the model is generally weak. We also compute approximate changes in estimated cosmological parameters in the broken-isotropy models. Only the overall normalization of the power spectrum is modified significantly.Comment: Accepted for publication in Phys. Rev.

Feshbach resonances in ultracold ^{6,7}Li + ^{23}Na atomic mixtures

We report a theoretical study of Feshbach resonances in $^{6}$Li + $^{23}$Na and $^{7}$Li + $^{23}$Na mixtures at ultracold temperatures using new accurate interaction potentials in a full quantum coupled-channel calculation. Feshbach resonances for $l=0$ in the initial collisional open channel $^6$Li$(f=1/2, m_f=1/2) + ^{23}$Na$(f=1, m_f=1)$ are found to agree with previous measurements, leading to precise values of the singlet and triplet scattering lengths for the $^{6,7}$Li$+^{23}$Na pairs. We also predict additional Feshbach resonances within experimentally attainable magnetic fields for other collision channels.Comment: 4 pages, 3 figure

Ro-vibrational relaxation of HCN in collisions with He: Rigid bender treatment of the bending-rotation interaction

We present a new theoretical method to treat atom-rigid bender inelastic collisions at the Close Coupling level (RBCC) in the space fixed frame. The coupling between rotation and bending is treated exactly within the rigid bender approximation and we obtain the cross section for the rotational transition between levels belonging to different bending levels. The results of this approach are compared with those obtained when using the rigid bender averaged approximation (RBAA) introduced in our previous work dedicated to this system. We discuss the validity of this approximation and of the previous studies based on rigid linear HCN

Isotopic replacement in ionic systems: the 4He2+ + 3He -> 3He4He+ + 4He reaction

Full quantum dynamics calculations have been carried out for the ionic reaction 4He2+ + 3He and state-to-state reactive probabilities have been obtained using both a time-dependent (TD) and a time-independent (TI) approach. An accurate ab-initio potential energy surface has been employed for the present quantum dynamics and the two sets of results are shown to be in agreement with each other. The results for zero total angular momentum suggest a marked presence of atom exchange (isotopic replacement) reaction with probabilities as high as 60%. The reaction probabilities are only weakly dependent on the initial vibrational state of the reactants while they are slightly more sensitive to the degree of rotational excitation. A brief discussion of the results for selected higher total angular momentum values is also presented, while the l-shifting approximation [1] has been used to provide estimates of the total reaction rates for the title process. Such rates are found to be large enough to possibly become experimentally accessible

Total angular momentum representation for atom-molecule collisions in electric fields

It is shown that the atom-molecule collision problem in the presence of an external electric field can be solved using the total angular momentum representation in the body-fixed coordinated frame, leading to a computationally efficient method for ab initio modeling of low-temperature scattering phenomena. Our calculations demonstrate rapid convergence of the cross sections for vibrational and Stark relaxation in He-CaD collisions with the number of total angular momentum states in the basis set, leading to a 5-100 fold increase in computational efficiency over the previously used methods based on the fully uncoupled space-fixed representation. These results open up the possibility of carrying out numerically converged quantum scattering calculations on a wide array of atom-molecule collisions and chemical reactions in the presence of electric fields.Comment: 19 pages, 3 figures, 1 tabl

Non-adiabatic effects in long-pulse mixed-field orientation of a linear polar molecule

We present a theoretical study of the impact of an electrostatic field combined with non-resonant linearly polarized laser pulses on the rotational dynamics of linear molecules. Within the rigid rotor approximation, we solve the time-dependent Schr\"odinger equation for several field configurations. Using the OCS molecule as prototype, the field-dressed dynamics is analyzed in detail for experimentally accessible static field strengths and laser pulses. Results for directional cosines are presented and compared to the predictions of the adiabatic theory. We demonstrate that for prototypical field configuration used in current mixed-field orientation experiments, the molecular field dynamics is, in general, non-adiabatic, being mandatory a time-dependent description of these systems. We investigate several field regimes identifying the sources of non-adiabatic effects, and provide the field parameters under which the adiabatic dynamics would be achieved.Comment: 16 pages, 16 figures. Submitted to Physical Review

Extension of the Morris-Shore transformation to multilevel ladders

We describe situations in which chains of N degenerate quantum energy levels, coupled by time-dependent external fields, can be replaced by independent sets of chains of length N, N-1,...,2 and sets of uncoupled single states. The transformation is a generalization of the two-level Morris-Shore transformation [J.R. Morris and B.W. Shore, Phys. Rev. A 27, 906 (1983)]. We illustrate the procedure with examples of three-level chains