Probing Low-Energy Resonances in Water-Hydrogen Inelastic Collisions.

Molecular scattering at collisional energies of the order of 10-100 cm^{-1} (corresponding to kinetic temperatures in the 15-150 K range) provides insight into the details of the scattering process and, in particular, of the various resonances that appear in inelastic cross sections. In this Letter, we present a detailed experimental and theoretical study of the rotationally inelastic scattering of ground-state ortho-D_{2}O by ground-state para-H_{2} in the threshold region of the D_{2}O(0_{00}→2_{02}) transition at 35.9 cm^{-1}. The measurements were performed with a molecular crossed beam apparatus with variable collision angle, thence with variable collisional energy. Calculations were carried out with the coupled-channel method combined with a dedicated high-level D_{2}O-H_{2} intermolecular potential. Our theoretical cross section 0_{00}→2_{02} is found to display several resonance peaks in perfect agreement with the experimental work, in their absolute positions and relative intensities. We show that those peaks are mostly due to shape resonances, characterized here for the first time for a polyatomic molecule colliding with a diatom.

Rotational quenching of an interstellar gas thermometer: CH3CNHe collisions.

Among all the molecular species found in the interstellar medium, molecules with threefold symmetry axes play a special role, as their rotational spectroscopy allows them to act as practical gas thermometers. Methyl-cyanide (CH3CN) is the second most abundant of those (after ammonia). We compute in this paper the collisional dynamics of methyl-cyanide in collision with helium, for both the A- and the E-symmetries of CH3CN. The potential energy surface is determined using the CCSD(T)-F12b formalism and fit with convenient analytic functions. We compute the rotationally inelastic cross sections for all levels up to 510 cm-1 of collision energy, employing at low energy exact Coupled Channels methods, and at higher energies, approximate Coupled States methods. For temperatures from 7 K up to 300 K, rates of quenching are computed and most are found to differ from those reported earlier (up to a factor of a thousand), calling for a possible reexamination of the temperatures assigned to low density gasses.

Interaction of the simple carbene c-C3H2 with H2: potential energy surface and low-energy scattering.

Cyclopropenylidene, c-C3H2, is a simple hydrocarbon, ubiquitous in astrophysical gases, and possessing a permanent electric dipole moment. Its readily observed rotational transitions make it an excellent probe for the physics and history of interstellar matter. The collisional properties of c-C3H2 with the main background gas, H2, are computed here. We present a full 5-D Potential Energy Surface in the rigid molecule approach, and fit it to relevant functionals for subsequent scattering. We perform low-energy quantum scattering at energies less than 50 cm-1. We use both ortho and para H2 as projectiles. We determine the quality of the various approximations to exact coupled channel scattering and examine paths to go towards higher energy scattering relevant for astrophysics. We compare the results obtained here with earlier ones for scattering with helium.

Rotational (de)-excitation of cyclic and linear C3H2 by collision with He.

Among the closed-shell hydrocarbons, the carbenes c- and l-C3H2 are the lightest ones to display a permanent electric dipole moment and be detectable by rotational spectroscopy. The cyclic form, cyclopropenylidene, is ubiquitous in the InterStellar Matter (ISM) of the Milky Way and external galaxies. As such, it serves as a marker to help in characterizing the physical conditions of the ISM. The linear form, propadienylidene, is less abundant. In order to get access to their absolute and relative abundances, it is essential to understand their collisional excitation/quenching schemes. We compute here a precise ab initio potential energy surface for the interaction of c- and l-C3H2 with helium, by means of a CCSD(T)-F12a formalism and a fit onto relevant spherical harmonics functions. We conduct quantum dynamical scattering in order to get precise cross sections using a coupled-channel approach for solving the nuclear motion. We average sections to have rates for rotational quenching from 5 to 150 K. We show that these new rates are vastly different, up to more than an order of magnitude, from the older rates presented in the literature, computed with angular momentum algebra only. We expect large differences in the astrophysical analyses of C3H2, including the chemical history of those ubiquitous carbenes.

The HCO⁺-H2 van der Waals interaction: potential energy and scattering.

We compute the rigid-body, four-dimensional interaction potential between HCO(+) and H2. The ab initio energies are obtained at the coupled-cluster single double triple level of theory, corrected for Basis Set Superposition Errors. The ab initio points are fit onto the spherical basis relevant for quantum scattering. We present elastic and rotationally inelastic coupled channels scattering between low lying rotational levels of HCO(+) and para-/ortho-H2. Results are compared with similar earlier computations with He or isotropic para-H2 as the projectile. Computations agree with earlier pressure broadening measurements.

State-to-state differential and relative integral cross sections for rotationally inelastic scattering of H2O by hydrogen.

State-to-state differential cross sections (DCSs) for rotationally inelastic scattering of H(2)O by H(2) have been measured at 71.2 meV (574 cm(-1)) and 44.8 meV (361 cm(-1)) collision energy using crossed molecular beams combined with velocity map imaging. A molecular beam containing variable compositions of the (J = 0, 1, 2) rotational states of hydrogen collides with a molecular beam of argon seeded with water vapor that is cooled by supersonic expansion to its lowest para or ortho rotational levels (J(KaKc) = 0(00) and 1(01), respectively). Angular speed distributions of fully specified rotationally excited final states are obtained using velocity map imaging. Relative integral cross sections are obtained by integrating the DCSs taken with the same experimental conditions. Experimental state-specific DCSs are compared with predictions from fully quantum scattering calculations on the most complete H(2)O-H(2) potential energy surface. Comparison of relative total cross sections and state-specific DCSs show excellent agreement with theory in almost all details.

Communication: Mapping water collisions for interstellar space conditions.

We report a joint experimental and theoretical study that directly tests the quality of the potential energy surfaces used to calculate energy changing cross sections of water in collision with helium and molecular hydrogen, at conditions relevant for astrophysics. Fully state-to-state differential cross sections are measured for H(2)O-He and H(2)O-H(2) collisions at 429 and 575 cm(-1) collision energy, respectively. We compare these differential cross sections with theoretical ones for H(2)O+H(2) derived from state-of-the-art potential energy surfaces [P. Valiron et al., J. Chem. Phys. 129, 134306 (2008)] and quantum scattering calculations. This detailed comparison forms a stringent test of the validity of astrophysics calculations for energy changing rates in water. The agreement between theory and experiment is striking for most of the state-to-state differential cross sections measured.

A five-dimensional potential-energy surface for the rotational excitation of SO2 by H2 at low temperatures.

The SO(2) molecule is detected in a large variety of astronomical objects, notably molecular clouds and star-forming regions. An accurate modeling of the observations needs a very good knowledge of the collisional excitation rates with H(2) because of competition between collisional and radiative processes that excite and quench the different rotational levels of SO(2). We report here a five-dimensional, rigid-body, interaction potential for SO(2)-H(2). As a first application, we present rate constants for excitation/de-excitation of the 31 first levels of SO(2) by para-H(2) at low temperatures. Propensity rules are discussed.

Topological aspects of chaotic scattering in higher dimensions.

We investigate the topological properties of the chaotic invariant set associated with the dynamics of scattering systems with three or more degrees of freedom. We show that the separation of one degree of freedom from the rest in the asymptotic regime, a common property in a large class of scattering models, defines a gate which is a dynamical object with phase space separating invariant manifolds. The manifolds form an invariant set causing singularities in the scattering process. The codimension one property of the manifolds ensures that the fractal structure of the invariant set can be studied by scattering functions defined over simple one-dimensional families of initial conditions as usually done in two-degree-of-freedom scattering problems. It is found that the fractal dimension of the invariant set is not due to the gates but to interior hyperbolic periodic orbits.

Parity non conservation: NMR parameters in chiral molecules.

The formula giving the parity-violating electroweak interaction contribution to the magnetic shielding tensor has been applied to enantiomers containing thallium. Using an extended Hückel relativistically parameterized method a chemical shift difference close to 1 mHz at 11.7 T is calculated in two couples of enantiomers. Such a difference is slightly lower than the extreme line width which may be actually reached in ultra-high resolution NMR.

Staphylococcus epidermidis biofilms: unexpected outcome of double and triple antibiotic combinations with rifampin.

Staphylococcus epidermidis, in contact with artificial surfaces, may produce a protective glue-like matrix or biofilm. The authors demonstrated that rifampin alone among 35 antibiotics penetrated the biofilm within a 24 hr exposure producing a major but incomplete killing. Antibiotics of the cell-wall active class (including vancomycin) were synergistic with rifampin, completing the bactericidal action. The addition of these antibiotics to a rifampin-vancomycin combination did not alter the synergy. Other antibiotics (including aminoglycosides) antagonized rifampin activity. This antagonism of rifampin was maintained when the antibiotics were added to the rifampin-vancomycin synergistic combination. These results may have implications for the choice of optimal therapeutic regimens in the management of implant-associated infection.

Impenetrable barriers in phase-space.

Dynamical systems theory is used to construct a general phase-space version of transition state theory. Special multidimensional separatrices are found which act as impenetrable barriers in phase-space between reacting and nonreacting trajectories. The elusive momentum-dependent transition state between reactants and products is thereby characterized. A practical algorithm is presented and applied to a strongly coupled Hamiltonian.