Computational study of the rovibrational spectrum of H2O-HF

In this paper we report rovibrational energy levels, transition frequencies, and intensities computed for H2O-HF using a new ab initio potential energy surface and compare with available experimental data. We use the rigid monomer approximation. A G4 symmetry-adapted Lanczos algorithm and an uncoupled product basis are employed. The rovibrational levels are computed up to J = 4. The new analytic 9-D potential is �t to 39771 counterpoise corrected CCSD(T)(F12*)/augcc- pVTZ energies and reduces to the sum of uncoupled H2O and HF potentials in the dissociation limit. On the new potential better agreement with experiment is obtained by re-assigning the R(1) transitions of two vibrational states.

Low-Lying Electronic States of the Nickel Dimer

The generalized Van Vleck second order multireference perturbation theory (GVVPT2) method was used to investigate the low-lying electronic states of Ni2. Because the nickel atom has an excitation energy of only 0.025 eV to its first excited state (the least in the first row of transition elements), Ni2 has a particularly large number of low-lying states. Full potential energy curves (PECs) of more than a dozen low-lying electronic states of Ni2, resulting from the atomic combinations 3F4 + 3F4 and 3D3 + 3D3, were computed. In agreement with previous theoretical studies, we found the lowest lying states of Ni2 to correlate with the 3D3 + 3D3 dissociation limit, and the holes in the d-subshells were in the subspace of delta orbitals (i.e., the so-dubbed δδ-states). In particular, the ground state was determined as X 1Γg and had spectroscopic constants: bond length (Re) = 2.26 Å, harmonic frequency (ωe) = 276.0 cm−1, and binding energy (De) = 1.75 eV; whereas the 1 1Σg+ excited state (with spectroscopic constants: Re = 2.26 Å, ωe = 276.8 cm−1, and De = 1.75) of the 3D3 + 3D3 dissociation channel lay at only 16.4 cm−1 (0.002 eV) above the ground state at the equilibrium geometry. Inclusion of scalar relativistic effects through the spin-free exact two component (sf-X2C) method reduced the bond lengths of both of these two states to 2.20 Å, and increased their binding energies to 1.95 eV and harmonic frequencies to 296.0 cm−1 for X 1Γg and 297.0 cm−1 for 1 1Σg+. These values are in good agreement with experimental values of Re = 2.1545 ± 0.0004 Å, ωe = 280 ± 20 cm−1, and D0 = 2.042 ± 0.002 eV for the ground state. All states considered within the 3F4 + 3F4 dissociation channel proved to be energetically high-lying and van der Waals-like in nature. In contrast to most previous theoretical studies of Ni2, full PECs of all considered electronic states of the molecule were produced.

Modeling disk fragmentation and multiplicity in massive star formation

Context. There is growing evidence that massive stars grow by disk accretion in a similar way to their low-mass counterparts. Early in evolution, these disks can achieve masses that are comparable to the current stellar mass, and therefore the forming disks are highly susceptible to gravitational fragmentation. Aims. We investigate the formation and early evolution of an accretion disk around a forming massive protostar, focussing on its fragmentation physics. To this end, we follow the collapse of a molecular cloud of gas and dust, the formation of a massive protostar, the formation of its circumstellar disk, and the formation and evolution of the disk fragments. Methods. We used a grid-based, self-gravity radiation hydrodynamics code including a sub-grid module for stellar evolution and dust evolution. We purposely do not use a sub-grid module for fragmentation such as sink particles to allow for all paths of fragment formation and destruction, but instead we keep the spatial grid resolution high enough to properly resolve the physical length scales of the problem, namely the pressure scale height and Jeans length of the disk. Simulations are performed on a grid in spherical coordinates with a logarithmic spacing of the grid cells in the radial direction and a cosine distribution of the grid cells in the polar direction, focusing the spatial resolution on the disk midplane. As a consequence, roughly 25% of the total number of grid cells, corresponding to ~26 million grid cells, are used to model the disk physics. These constitute the highest resolution simulations performed up to now on disk fragmentation around a forming massive star with the physics considered here. For a better understanding of the effects of spatial resolution and to compare our high-resolution results with previous lower resolution studies in the literature, we perform the same simulation at five different resolutions, each run differing in resolution from its predecessor by a factor of two. Results. The cloud collapses and a massive (proto)star is formed in its center surrounded by a fragmenting Keplerian-like accretion disk with spiral arms. The fragments have masses of ~1 M⊙, and their continuous interactions with the disk, spiral arms, and other fragments result in eccentric orbits. Fragments form hydrostatic cores surrounded by secondary disks with spiral arms that also produce new fragments. We identified several mechanisms of fragment formation, interaction, and destruction. Central temperatures of the fragments can reach the hydrogen dissociation limit, form second Larson cores, and evolve into companion stars. Based on this, we study the multiplicity predicted by the simulations and find approximately six companions at different distances from the primary: from possible spectroscopic multiples, to companions at distances between 1000 and 2000 au.

Low-temperature rate constants and radiative transfer for rotational de-excitation of C5S by collision with He

ABSTRACT The C5S molecule is the largest member of the series of sulphur-containing carbon chains CnS observed in space. Given the lack of data concerning this molecule, we computed rate coefficients of C5S(1Σ+) induced by collision with He. These rates are obtained for thermal temperature below 100 K by mean of a new two-dimensional potential energy surface (PES) calculated with the explicit correlated coupled cluster with single, double, and pertubative triple excitation (ccsd(t)-f12) ab initio approach and the aug-cc-pVTZ basis sets. The C5S–He PES presents three minimums of −59.726, −55.355, and −36.506 cm−1 below its dissociation limit. Using this PES, the integral cross-sections are performed in the close-coupling (CC) and coupled-state (CS) quantum time independent formalisms for $E_\mathrm{ c}\le 500 \, \mathrm{ cm}^{-1}$ and J ≤ 13 (for CC) and J ≤ 50 (for CS). By averaging these cross-sections we obtained the downward rate coefficients. The new collisional data are used to simulate the excitation of C5S in the circumstellar gas. We obtain the excitation and brightness temperatures of the four lines observed towards the IRC+10216 which confirms the necessity of using radiative transfer calculations to accurately determine C5S abundance since the local thermodynamic equilibrium conditions are not fulfilled. The new collisional data should help to estimate the abundance of C5S in several interstellar regions.

Long-range potentials and dipole moments of the CO electronic states converging to the ground dissociation limit

The potential-energy and dipole-moment functions for six electronic states are obtained both analytically, in the framework of long-range perturbation theory, and numerically, by using first-principles methods.

Hyperfine structure of the NaCs b3Π2 state near the dissociation limit 3S1/2 + 6P3/2 observed with ultracold atomic photoassociation

The hyperfine structure of the ultracold NaCs molecular b3Π2 state is studied experimentally and theoretically.