Dynamical Effective Field Model for Interacting Ferrofluids: II. The proper relaxation time and effects of dynamic correlations

The recently proposed dynamical effective field model (DEFM) is quantitatively accurate for ferrofluid dynamics. It is derived in paper I within the framework of dynamical density functional theory (DDFT) along with a phenomenological description of nonadiabatic effects. However, it remains to clarify how the characteristic rotational relaxation time of a dressed particle, denoted by τr, is quantitatively related to that of a bare particle, denoted by τr0. By building macro-micro connections via two different routes, I reveal that under some gentle assumptions τr can be identified with the mean time characterizing long-time rotational self-diffusion. I further introduce two simple but useful integrated correlation factors, describing the effects of quasi-static (adiabatic) and dynamic (nonadiabatic) inter-particle correlations, respectively. In terms of both the dynamic magnetic susceptibility is expressed in an illuminating and elegant form. Remarkably, it shows that the macro-micro connection is established via two successive steps: a dynamical coarse-graining with nonadiabatic effects accounted for by the dynamic factor, followed by equilibrium ensemble averaging captured by the static factor. By analyzing data from Brownian dynamics simulations on monodisperse interacting ferrofluids, I find τr/τr0 is, somehow unexpectedly, insensitive to changes of particle volume fraction. A physical picture is proposed to explain it. Furthermore, an empirical formula is proposed to characterize the dependence of τr/τr0 on dipole-dipole interaction strength. The DEFM supplemented with this formula leads to parameter-free predictions in good agreement with results from Brownian dynamics simulations. The theoretical developments presented in this paper may have important consequences to studies of ferrofluid dynamics in particular and other systems modelled by DDFTs in general.

Experimental investigations on rotation–vibration energy transfer in H2-N2 collisions

We investigated the rotational-vibrational impact energy transfer processes in a H2–N2 gas mixture system. The stimulated Raman pumping technique was used to excite H2 molecules to the (1,7) high rotational states. The population of the H2(1,7) level was verified by the coherent anti-Stokes Raman (CARS) spectra, the total pressure of the mixture was maintained at 500 Torr, and nitrogen with different molar ratios was filled in the sample cell. The collisional deactivation rate coefficients of the excited state H2(1,7) with H2 and N2 were obtained by fitting the experimental data with the Stern–Volmer equation. The multi-quantum near-resonant rotational relaxation process of H2(1, 7) colliding with N2 was confirmed by the time-resolved CARS profile measurements of H2(v=1, J=7, 5, 3) after the excitation of H2(1, 7).

Rotational relaxation of HCO+ and DCO+ by collision with H2

ABSTRACT The HCO+ and DCO+ molecules are commonly used as tracers in the interstellar medium. Therefore, accurate rotational rate coefficients of these systems with He and H2 are crucial in non-local thermal equilibrium models. We determine in this work the rotational de-excitation rate coefficients of HCO+ in collision with both para- and ortho-H2, and also analyse the isotopic effects by studying the case of DCO+. A new four-dimensional potential energy surface from ab initio calculations was developed for the HCO+–H2 system, and adapted to the DCO+–H2 case. These surfaces are then employed in close-coupling calculations to determine the rotational de-excitation cross-sections and rate coefficients for the lower rotational states of HCO+ and DCO+. The new rate coefficients for HCO+ + para-H2 were compared with the available data, and a set of rate coefficients for HCO+ + ortho-H2 is also reported. The difference between the collision rates with ortho- and para-H2 is found to be small. These calculations confirm that the use of the rate coefficients for HCO+ + para-H2 for estimating those for HCO+ + ortho-H2 as well as for DCO+ + para-H2 is a good approximation.