Search

Modeling environments that are not in local thermal equilibrium, such as protoplanetary disks or planetary atmospheres, with molecular spectroscopic data from space telescopes requires knowledge of the rate coefficients of rovibrationally inelastic molecular collisions. Here, we present such rate coefficients in a temperature range from 10 to 500 K for collisions of CO$_2$ with He atoms in which CO$_2$ is (de)excited in the bend mode. They are obtained from numerically exact coupled-channel (CC) calculations as well as from calculations with the less demanding coupled-states approximation (CSA) and the vibrational close-coupling rotational infinite-order sudden (VCC-IOS) method. All of the calculations are based on a newly calculated accurate ab initio four-dimensional CO$_2$-He potential surface including the CO$_2$ bend ($\nu_2$) mode. We find that the rovibrationally inelastic collision cross sections and rate coefficients from the CSA and VCC-IOS calculations agree to within 50% with the CC results at the rotational state-to-state level, except for the smaller ones and in the low energy resonance region, and to within 20% for the overall vibrational quenching rates except for temperatures below 50 K where resonances provide a substantial contribution. Our CC quenching rates agree with the most recent experimental data within the error bars. We also compared our results with data from Clary et al. calculated in the 1980's with the CSA and VCC-IOS methods and a simple atom-atom model potential based on ab initio Hartree-Fock calculations and found that their cross sections agree fairly well with ours for collision energies above 500 cm$^{-1}$, but that the inclusion of long range attractive dispersion interactions is crucial to obtain reliable cross sections at lower energies and rate coefficients at lower temperatures., Comment: The article has been accepted to the Journal of Chemical Physics

Collisions between cold polar molecules represent a fascinating research frontier, but have proven hard to probe experimentally. We report measurements of inelastic cross sections for collisions between NO and ND 3 molecules at energies between 0.1 and 580 cm-1 , with full quantum state resolution. At energies below the 100 cm-1 well depth of the interaction potential, we observed backward glories originating from peculiar U-turn trajectories. At energies below 0.2 cm-1, we observed a breakdown of the Langevin capture model, which we interpreted in terms of a suppressed mutual polarization during the collision, effectively switching off the molecular dipole moments. Scattering calculations based on an ab initio NO-ND3 potential energy surface revealed the crucial role of near-degenerate rotational levels with opposite parity in low-energy dipolar collisions.

Feshbach resonances are fundamental to interparticle interactions and become particularly important in cold collisions with atoms, ions, and molecules. Here we present the detection of Feshbach resonances in a benchmark system for strongly interacting and highly anisotropic collisions -- molecular hydrogen ions colliding with noble gas atoms. The collisions are launched by cold Penning ionization exclusively populating Feshbach resonances that span both short- and long-range parts of the interaction potential. We resolved all final molecular channels in a tomographic manner using ion-electron coincidence detection. We demonstrate the non-statistical nature of the final state distribution. By performing quantum scattering calculations on ab initio potential energy surfaces, we show that the isolation of the Feshbach resonance pathways reveals their distinctive fingerprints in the collision outcome.

Astrophysical modeling of processes in environments that are not in local thermal equilibrium requires the knowledge of state-to-state rate coefficients of rovibrational transitions in molecular collisions. These rate coefficients can be obtained from coupled-channel (CC) quantum scattering calculations which are very demanding, however. Here we present various approximate, but more efficient methods based on the coupled-states approximation (CSA) which neglects the off-diagonal Coriolis coupling in the scattering Hamiltonian in body-fixed coordinates. In particular, we investigated a method called NNCC (nearest-neighbor Coriolis coupling) [D. Yang, X. Hu, D. H. Zhang, and D. Xie, J. Chem. Phys. 148, 084101 (2018)] that includes Coriolis coupling to first order. The NNCC method is more demanding than the common CSA method, but still much more efficient than full CC calculations, and it is substantially more accurate than CSA. All of this is illustrated by showing state-to-state cross sections and rate coefficients of rovibrational transitions induced in CO$_2$ by collisions with He atoms. It is also shown that a further reduction of CPU time, practically without loss of accuracy, can be obtained by combining the NNCC method with the multi-channel distorted-wave Born approximation (MC-DWBA) that we applied in full CC calculations in a previous paper., Comment: This article has been accepted at the Journal of Chemical Physics (JCP)

One of the most important parameters in a collision is the 'miss distance' or impact parameter, which in quantum mechanics is described by quantized partial waves. Usually, the collision outcome is the result of unavoidable averaging over many partial waves. Here we present a study of low-energy NO\textendash He collisions, that enables us to probe how individual partial waves evolve during the collision. By tuning the collision energies to scattering resonances between 0.4 and 6 cm$^{-1}$, the initial conditions are characterized by a limited set of partial waves. By preparing NO in a rotationally excited state before the collision and by studying rotational de-excitation collisions, we were able to add one quantum of angular momentum to the system and trace how it evolves. Distinct fingerprints in the differential cross sections yield a comprehensive picture of the partial wave dynamics during the scattering process. Exploiting the principle of detailed balance, we show that rotational de-excitation collisions probe time-reversed excitation processes with superior energy and angular resolution., Comment: 18 pages, 4 figures

The experimental characterization of scattering resonances in low energy collisions has proven to be a stringent test for quantum chemistry calculations. Previous measurements on the NO-H$_2$ system at energies down to $10$ cm$^{-1}$ challenged the most sophisticated calculations of potential energy surfaces available. In this report, we continue these investigations by measuring the scattering behavior of the NO-H$_2$ system in the previously unexplored $0.4 - 10$ cm$^{-1}$ region for the parity changing de-excitation channel of NO. We study state-specific inelastic collisions with both \textit{para}- and \textit{ortho}-H$_2$ in a crossed molecular beam experiment involving Stark deceleration and velocity map imaging. We are able to resolve resonance features in the measured integral and differential cross sections. Results are compared to predictions from two previously available potential energy surfaces and we are able to clearly discriminate between the two potentials. We furthermore identify the partial wave contributions to these resonances, and investigate the nature of the differences between collisions with \textit{para}- and \textit{ortho}-H$_2$. Additionally, we tune the energy spreads in the experiment to our advantage to probe scattering behavior at energies beyond our mean experimental limit., Comment: The following article has been submitted to the Journal of Chemical Physics. 8 pages, 8 figures

The pathway toward the tailored synthesis of materials starts with precise characterization of the conformational properties and dynamics of individual molecules. Electron spin resonance based scanning tunneling microscopy can potentially address molecular structure with unprecedented resolution. Here, we determine the fine structure and geometry of an individual TiH molecule, utilizing a combination of a newly developed mK ESR-STM in a vector magnetic field and ab initio approaches. We demonstrate a strikingly large anisotropy of the g-tensor unusual for a spin doublet ground state, resulting from a non-trivial orbital angular momentum stemming from the molecular ground state. We quantify the relationship between the resultant fine structure, hindered rotational modes, and orbital excitations. Our model system provides new avenues to determine the structure and dynamics of individual molecules.

At low energies, the quantum wave-like nature of molecular interactions result in unique scattering behavior, ranging from the universal Wigner laws near zero Kelvin to the occurrence of scattering resonances at higher energies. It has proven challenging to experimentally probe the individual waves underlying these phenomena. We report measurements of state-to-state integral and differential cross sections for inelastic NO-He collisions in the 0.2 - 8.5 cm$^{-1}$ range with 0.02 cm$^{-1}$ resolution. We study the onset of the resonance regime by probing the lowest-lying resonance dominated by s and p waves only. The highly structured differential cross sections directly reflect the increasing number of contributing waves as the energy is increased. A new NO-He potential calculated at the CCSDT(Q) level was required to reproduce our measurements., Comment: 14 pages, 4 figures

Scattering resonances play a central role in collision processes in physics and chemistry. They help building an intuitive understanding of the collision dynamics due to the spatial localization of the scattering wavefunctions. For resonances that are localized in the reaction region, located at short separation behind the centrifugal barrier, sharp peaks in the reaction rates are the characteristic signature, observed recently with state-of-the-art experiments in low energy collisions. If, however, the localization occurs outside of the reaction region, mostly the elastic scattering is modified. This may occur due to above barrier resonances, the quantum analogue of classical orbiting. By probing both elastic and inelastic scattering of metastable helium with deuterium molecules in merged beam experiments, we differentiate between the nature of quantum resonances -- tunneling vs above barrier -- and corroborate our findings by calculating the corresponding scattering wavefunctions., Comment: 15 pages, 6 figures

A new analytical potential energy surface (PES) has been constructed for H$_2^+$-He using a reproducing kernel Hilbert space (RKHS) representation from an extensive number of $ab initio$ energies computed at the multi-reference and full configuration interaction level of theory. For the MRCI PES the long-range interaction region of the PES is described by analytical functions and is connected smoothly to the short-range interaction region, represented as a RKHS. All ro-vibrational states for the ground electronic state of H$_2^+$-He are calculated using two different methods to determine quantum bound states. Comparing transition frequencies for the near-dissociation states for $ortho$- and $para$-H$_2^+$-He allows assignment of the 15.2 GHz line to a $J=2$ $e/f$ parity doublet of $ortho$-H$_2^+$-He whereas the experimentally determined 21.8 GHz line is only consistent with a $(J=0)$ $\rightarrow$ $(J=1)$ $e/e$ transition in $para$-H$_2^+$-He., Comment: 21 pages, 7 figures, 1 supporting information file

Whereas collisions between atoms and molecules are largely understood, collisions between two molecules have proven much harder to study. In both experiment and theory, our ability to determine quantum state-resolved bimolecular cross sections lags behind their atom-molecule counterparts by decades. For many bimolecular systems, even rules of thumb -- much less intuitive understanding -- of scattering cross sections are lacking. Here, we report the measurement of state-to-state differential cross sections on the collision of state-selected and velocity-controlled nitric oxide (NO) radicals and oxygen (O2) molecules. Using velocity map imaging of the scattered NO radicals, the full product-pair correlations of rotational excitation that occurs in both collision partners from individual encounters are revealed. The correlated cross sections show surprisingly good agreement with quantum scattering calculations using ab initio NO-O2 potential energy surfaces. The observations show that the well-known energy-gap law that governs atom-molecule collisions does not generally apply to bimolecular excitation processes, and reveal a propensity rule for the vector correlation of product angular momenta., Comment: Received: 06 September 2017 Accepted: 20 December 2017 Published online: 19 February 2018, Nature Chemistry 2018

Magnetic fields play an important role during star formation. Direct magnetic field strength observations have proven specifically challenging in the extremely dynamic protostellar phase. Because of their occurrence in the densest parts of star forming regions, masers, through polarization observations, are the main source of magnetic field strength and morphology measurements around protostars. Of all maser species, methanol is one of the strongest and most abundant tracers of gas around high-mass protostellar disks and in outflows. However, as experimental determination of the magnetic characteristics of methanol has remained largely unsuccessful, a robust magnetic field strength analysis of these regions could hitherto not be performed. Here we report a quantitative theoretical model of the magnetic properties of methanol, including the complicated hyperfine structure that results from its internal rotation. We show that the large range in values of the Land\'{e} g-factors of the hyperfine components of each maser line lead to conclusions which differ substantially from the current interpretation based on a single effective g-factor. These conclusions are more consistent with other observations and confirm the presence of dynamically important magnetic fields around protostars. Additionally, our calculations show that (non-linear) Zeeman effects must be taken into account to further enhance the accuracy of cosmological electron-to-proton mass ratio determinations using methanol., Comment: 23 pages, 3 figures, excluding Supplementary information. Author manuscript version before editorial/copyediting by Nature Astronomy. Journal version available via http://rdcu.be/FPeB . Supplementary material available via https://static-content.springer.com/esm/art%3A10.1038%2Fs41550-017-0341-8/MediaObjects/41550_2017_341_MOESM1_ESM.pdf

We study collisions between neutral, deuterated ammonia molecules (ND$_3$) stored in a 50 cm diameter synchrotron and argon atoms in co-propagating supersonic beams. The advantages of using a synchrotron in collision studies are twofold: (i) By storing ammonia molecules many round-trips, the sensitivity to collisions is greatly enhanced; (ii) The collision partners move in the same direction as the stored molecules, resulting in low collision energies. We tune the collision energy in three different ways: by varying the velocity of the stored ammonia packets, by varying the temperature of the pulsed valve that releases the argon atoms, and by varying the timing between the supersonic argon beam and the stored ammonia packets. These give consistent results. We determine the relative, total, integrated cross-section for $\mathrm{ND}_3+\mathrm{Ar}$ collisions in the energy range of 40-140 cm$^{-1}$, with a resolution of 5-10 cm$^{-1}$ and an uncertainty of 7-15%. Our measurements are in good agreement with theoretical scattering calculations.

Because of the very peculiar conditions of chemistry in many astrophysical gases (low densities, mostly low temperatures, kinetics-dominated chemical evolution), great efforts have been devoted to study molecular signatures and chemical evolution. While experiments are being performed in many laboratories, it appears that the efforts directed towards theoretical works are not as strong. This report deals with the present status of chemical physics/physical chemistry theory, for the qualitative and quantitative understanding of kinetics of molecular scattering, being it reactive or inelastic. By gathering several types of expertise, from applied mathematics to physical chemistry, dialog is made possible, as a step towards new and more adapted theoretical frameworks, capable of meeting the theoretical, methodological and numerical challenges of kinetics-dominated gas phase chemistry in astrophysical environments. A state of the art panorama is presented, alongside present-day strengths and shortcomings. However, coverage is not complete, being limited in this report to actual attendance of the workshop. Some paths towards relevant progress are proposed., Comment: 24 pages, 7 figures. White paper reporting a workshop held in Garching, Nov 23-Dec 4, 2015

Anisotropy is a fundamental property of particle interactions. It occupies a central role in cold and ultra-cold molecular processes, where long range forces have been found to significantly depend on orientation in ultra-cold polar molecule collisions. Recent experiments have demonstrated the emergence of quantum phenomena such as scattering resonances in the cold collisions regime due to quantization of the intermolecular degrees of freedom. Although these states have been shown to be sensitive to interaction details, the effect of anisotropy on quantum resonances has eluded experimental observation so far. Here, we directly measure the anisotropy in atom-molecule interactions via quantum resonances by changing the quantum state of the internal molecular rotor. We observe that a quantum scattering resonance at a collision energy of $k_B$ x 270 mK appears in the Penning ionization of molecular hydrogen with metastable helium only if the molecule is rotationally excited. We use state of the art ab initio and multichannel quantum molecular dynamics calculations to show that the anisotropy contributes to the effective interaction only for $H_2$ molecules in the first excited rotational state, whereas rotationally ground state $H_2$ interacts purely isotropically with metastable helium. Control over the quantum state of the internal molecular rotation allows us to switch the anisotropy on or off and thus disentangle the isotropic and anisotropic parts of the interaction. These quantum phenomena provide a challenging benchmark for even the most advanced theoretical descriptions, highlighting the advantage of using cold collisions to advance the microscopic understanding of particle interactions., Comment: 19 pages, 3 figures

In molecular collisions, resonances occur at specific energies where the colliding particles temporarily form quasi-bound complexes, resulting in rapid variations in the energy dependence of scattering cross sections. Experimentally, it has proven challenging to observe such scattering resonances, especially in differential cross sections. We report the observation of resonance fingerprints in the state-to-state differential cross sections for inelastic NO-He collisions in the 13 to 19 cm$^{-1}$ energy range with 0.3 cm$^{-1}$ resolution. The observed structures were in excellent agreement with quantum scattering calculations. They were analyzed by separating the resonance contributions to the differential cross sections from the background through a partitioning of the multichannel scattering matrix. This revealed the partial wave composition of the resonances, and their evolution during the collision.

We present ultrahigh-resolution measurements of state-to-state inelastic differential cross sections for NO-Ne and NO-Ar collisions, obtained by combining the Stark deceleration and velocity map imaging techniques. We show that for counterpropagating crossed beam geometries, the effect of the velocity spreads of the reagent beams on the angular resolution of the images is minimized. Futhermore, the counterpropagating geometry results in images that are symmetric with respect to the relative velocity vector. This allows for the use of inverse Abel transformation methods that enhance the resolution further. State-resolved diffraction oscillations in the differential cross sections are measured with an angular resolution approaching 0.3$^\circ$. Distinct structures observed in the cross sections gauge the quality of recent \emph{ab initio} potential energy surfaces for NO-rare gas atom collisions with unprecedented precision.

We investigate the ultracold reaction dynamics of magnetically trapped NH($X ^3\Sigma^-$) radicals using rigorous quantum scattering calculations involving three coupled potential energy surfaces. We find that the reactive NH + NH cross section is driven by a short-ranged collisional mechanism, and its magnitude is only weakly dependent on magnetic field strength. Unlike most ultracold reactions observed so far, the NH + NH scattering dynamics is non-universal. Our results indicate that chemical reactions can cause more trap loss than spin-inelastic NH + NH collisions, making molecular evaporative cooling more difficult than previously anticipated., Comment: Supporting Information available from authors on request

Whereas atom-molecule collisions have been studied with complete quantum state resolution, interactions between two state-selected molecules have proven much harder to probe. Here, we report the measurement of state-resolved inelastic scattering cross sections for collisions between two open-shell molecules that are both prepared in a single quantum state. Stark-decelerated OH radicals were scattered with hexapole-focused NO radicals in a crossed beam configuration. Rotationally and spin-orbit inelastic scattering cross sections were measured on an absolute scale for collision energies between 70 and 300 cm$^{-1}$. These cross sections show fair agreement with quantum coupled-channels calculations using a set of coupled model potential energy surfaces based on ab initio calculations for the long-range non-adiabatic interactions and a simplistic short-range interaction. This comparison reveals the crucial role of electrostatic forces in complex molecular collision processes.

We report on the observation of magnetic dipole allowed transitions in the well-characterized $A\,^2\Sigma^+ - X\,^2\Pi$ band system of the OH radical. A Stark decelerator in combination with microwave Rabi spectroscopy is used to control the populations in selected hyperfine levels of both $\Lambda$-doublet components of the $X\,^2\Pi_{3/2},v=0,J=3/2$ ground state. Theoretical calculations presented in this paper predict that the magnetic dipole transitions in the $\nu'=1 \leftarrow \nu=0$ band are weaker than the electric dipole transitions by a factor of $2.58\times 10^3$ only, i.e., much less than commonly believed. Our experimental data confirm this prediction.

We present detailed calculations on resonances in rotationally and spin-orbit inelastic scattering of OH ($X\,^2\Pi, j=3/2, F_1, f$) radicals with He and Ne atoms. We calculate new \emph{ab initio} potential energy surfaces for OH-He, and the cross sections derived from these surfaces compare favorably with the recent crossed beam scattering experiment of Kirste \emph{et al.} [Phys. Rev. A \textbf{82}, 042717 (2010)]. We identify both shape and Feshbach resonances in the integral and differential state-to-state scattering cross sections, and we discuss the prospects for experimentally observing scattering resonances using Stark decelerated beams of OH radicals., Comment: 14 pages, 15 Figures

We theoretically study slow collisions of NH$_3$ molecules with He atoms, where we focus in particular on the observation of scattering resonances. We calculate state-to-state integral and differential cross sections for collision energies ranging from 10${}^{-4}$ cm$^{-1}$ to 130 cm$^{-1}$, using fully converged quantum close-coupling calculations. To describe the interaction between the NH${}_3$ molecules and the He atoms, we present a four-dimensional potential energy surface, based on an accurate fit of 4180 {\it ab initio} points. Prior to collision, we consider the ammonia molecules to be in their antisymmetric umbrella state with angular momentum $j=1$ and projection $k=1$, which is a suitable state for Stark deceleration. We find pronounced shape and Feshbach resonances, especially for inelastic collisions into the symmetric umbrella state with $j=k=1$. We analyze the observed resonant structures in detail by looking at scattering wavefunctions, phase shifts, and lifetimes. Finally, we discuss the prospects for observing the predicted scattering resonances in future crossed molecular beam experiments with a Stark-decelerated NH$_3$ beam., Comment: 17 pages, 12 figures

We present a detailed analysis of the role of the magnetic dipole-dipole interaction in cold and ultracold collisions. We focus on collisions between magnetically trapped NH molecules, but the theory is general for any two paramagnetic species for which the electronic spin and its space-fixed projection are (approximately) good quantum numbers. It is shown that dipolar spin relaxation is directly associated with magnetic-dipole induced avoided crossings that occur between different adiabatic potential curves. For a given collision energy and magnetic field strength, the cross-section contributions from different scattering channels depend strongly on whether or not the corresponding avoided crossings are energetically accessible. We find that the crossings become lower in energy as the magnetic field decreases, so that higher partial-wave scattering becomes increasingly important \textit{below} a certain magnetic field strength. In addition, we derive analytical cross-section expressions for dipolar spin relaxation based on the Born approximation and distorted-wave Born approximation. The validity regions of these analytical expressions are determined by comparison with the NH + NH cross sections obtained from full coupled-channel calculations. We find that the Born approximation is accurate over a wide range of energies and field strengths, but breaks down at high energies and high magnetic fields. The analytical distorted-wave Born approximation gives more accurate results in the case of s-wave scattering, but shows some significant discrepancies for the higher partial-wave channels. We thus conclude that the Born approximation gives generally more meaningful results than the distorted-wave Born approximation at the collision energies and fields considered in this work., Comment: Accepted by Eur. Phys. J. D for publication in Special Issue on Cold Quantum Matter - Achievements and Prospects (2011)

We present a combined experimental and theoretical study on the rotationally inelastic scattering of OH ($X\,^2\Pi_{3/2}, J=3/2, f$) radicals with the collision partners He, Ne, Ar, Kr, Xe, and D$_2$ as a function of the collision energy between $\sim 70$ cm$^{-1}$ and 400~cm$^{-1}$. The OH radicals are state selected and velocity tuned prior to the collision using a Stark decelerator, and field-free parity-resolved state-to-state inelastic relative scattering cross sections are measured in a crossed molecular beam configuration. For all OH-rare gas atom systems excellent agreement is obtained with the cross sections predicted by close-coupling scattering calculations based on accurate \emph{ab initio} potential energy surfaces. This series of experiments complements recent studies on the scattering of OH radicals with Xe [Gilijamse \emph{et al.}, Science {\bf 313}, 1617 (2006)], Ar [Scharfenberg \emph{et al.}, Phys. Chem. Chem. Phys. {\bf 12}, 10660 (2010)], He, and D$_2$ [Kirste \emph{et al.}, Phys. Rev. A {\bf 82}, 042717 (2010)]. A comparison of the relative scattering cross sections for this set of collision partners reveals interesting trends in the scattering behavior., Comment: 10 pages, 5 figures

Elastic and spin-changing inelastic collision cross sections are presented for cold and ultracold magnetically trapped NH. The cross sections are obtained from coupled-channel scattering calculations as a function of energy and magnetic field. We specifically investigate the influence of the intramolecular spin-spin, spin-rotation, and intermolecular magnetic dipole coupling on the collision dynamics. It is shown that $^{15}$NH is a very suitable candidate for evaporative cooling experiments. The dominant trap-loss mechanism in the ultracold regime originates from the intermolecular dipolar coupling term. At higher energies and fields, intramolecular spin-spin coupling becomes increasingly important. Our qualitative results and conclusions are fairly independent of the exact form of the potential and of the size of the channel basis set., Comment: Submitted to Phys. Rev. A

We present elastic and inelastic spin-changing cross sections for cold and ultracold NH($X\,^3\Sigma^-$) + NH($X\,^3\Sigma^-$) collisions, obtained from full quantum scattering calculations on an accurate \textit{ab initio} quintet potential-energy surface. Although we consider only collisions in zero field, we focus on the cross sections relevant for magnetic trapping experiments. It is shown that evaporative cooling of both fermionic $^{14}$NH and bosonic $^{15}$NH is likely to be successful for hyperfine states that allow for s-wave collisions. The calculated cross sections are very sensitive to the details of the interaction potential, due to the presence of (quasi-)bound state resonances. The remaining inaccuracy of the \textit{ab initio} potential-energy surface therefore gives rise to an uncertainty in the numerical cross-section values. However, based on a sampling of the uncertainty range of the \textit{ab initio} calculations, we conclude that the exact potential is likely to be such that the elastic-to-inelastic cross-section ratio is sufficiently large to achieve efficient evaporative cooling. This likelihood is only weakly dependent on the size of the channel basis set used in the scattering calculations.

We present four-dimensional ab initio potential energy surfaces for the three spin states of the NH-NH complex. The potentials are partially based on the work of Dhont et al. [J. Chem. Phys. 123, 184302 (2005)]. The surface for the quintet state is obtained at the RCCSD(T)/aug-cc-pVTZ level of theory and the energy diferences with the singlet and triplet states are calculated at the CASPTn/aug-cc-pVTZ (n = 2; 3) level of theory. The ab initio potentials are fitted to coupled spherical harmonics in the angular coordinates, and the long range is further expanded as a power series in 1/R. The RCCSD(T) potential is corrected for a size-consistency error prior to fitting. The long-range coeficients obtained from the fit are found to be in good agreement with perturbation theory calculations., Comment: submitted to JCP, supporting information available from authors on request