Floating in Space: How to Treat the Weak Interaction between CO Molecules in Interstellar Ices.

In the interstellar medium, six molecules have been conclusively detected in the solid state in interstellar ices, and a few dozen have been hypothesized and modeled to be present in the solid state as well. The icy mantles covering micrometer-sized dust grains are, in fact, thought to be at the core of complex molecule formation as a consequence of the local high density of molecules that are simultaneously adsorbed. From a structural perspective, the icy mantle is considered to be layered, with an amorphous water-rich inner layer surrounding the dust grain, covered by an amorphous CO-rich outer layer. Moreover, recent studies have suggested that the CO-rich layer might be crystalline and possibly even be segregated as a single crystal atop the ice mantle. If so, there are far-reaching consequences for the formation of more complex organic molecules, such as methanol and sugars, that use CO as a backbone. Validation of these claims requires further investigation, in particular on acquiring atomistic insight into surface processes, such as adsorption, diffusion, and reactivity on CO ices. Here, we present the first detailed computational study toward treating the weak interaction of (pure) CO ices. We provide a benchmark of the performance of various density functional theory methods in treating the binding of pure CO ices. Furthermore, we perform an atomistic and in-depth study of the binding energy of CO on amorphous and crystalline CO ices using a pair-potential-based force field. We find that CO adsorption is represented by a large distribution of binding energies (200-1600 K) on amorphous CO, including a significant amount of weak binding sites (<350 K). Increasing both the cluster size and the number of neighbors increases the mean of the observed binding energy distribution. Finally, we find that CO binding energies are dominated by dispersion and, as such, exchange-correlation functionals need to include a treatment of dispersion to accurately simulate surface processes on CO ices. In particular, we find the ωB97M-V functional to be a strong candidate for such simulations.

Imaging rotational energy transfer: comparative stereodynamics in CO + N2 and CO + CO inelastic scattering.

State-to-state rotational energy transfer in collisions of ground ro-vibrational state 13CO molecules with N2 molecules has been studied using the crossed molecular beam method under kinematically equivalent conditions used for 13CO + CO rotationally inelastic scattering described in a previously published report (Sun et al., Science, 2020, 369, 307-309). The collisionally excited 13CO molecule products are detected by the same (1 + 1' + 1'') VUV (Vacuum Ultra-Violet) resonance enhanced multiphoton ionization scheme coupled with velocity map ion imaging. We present differential cross sections and scattering angle resolved rotational angular momentum alignment moments extracted from experimentally measured 13CO + N2 scattering images and compare them with theoretical predictions from quasi-classical trajectories (QCT) on a newly calculated 13CO-N2 potential energy surface (PES). Good agreement between experiment and theory is found, which confirms the accuracy of the 13CO-N2 potential energy surface for the 1460 cm-1 collision energy studied by experiment. Experimental results for 13CO + N2 are compared with those for 13CO + CO collisions. The angle-resolved product rotational angular momentum alignment moments for the two scattering systems are very similar, which indicates that the collision induced alignment dynamics observed for both systems are dominated by a hard-shell nature. However, compared to the 13CO + CO measurements, the primary rainbow maximum in the DCSs for 13CO + N2 is peaked consistently at more backward scattering angles and the secondary maximum becomes much less obvious, implying that the 13CO-N2 PES is less anisotropic. In addition, a forward scattering component with high rotational excitation seen for 13CO + CO does not appear for 13CO-N2 in the experiment and is not predicted by QCT theory. Some of these differences in collision dynamics behaviour can be predicted by a comparison between the properties of the PESs for the two systems. More specific behaviour is also predicted from analysis of the dependence on the relative collision geometry of 13CO + N2 trajectories compared to 13CO + CO trajectories, which shows the special 'do-si-do' pathway invoked for 13CO + CO is not effective for 13CO + N2 collisions.

Molecular square dancing in CO-CO collisions.

Knowledge of rotational energy transfer (RET) involving carbon monoxide (CO) molecules is crucial for the interpretation of astrophysical data. As of now, our nearly perfect understanding of atom-molecule scattering shows that RET usually occurs by only a simple "bump" between partners. To advance molecular dynamics to the next step in complexity, we studied molecule-molecule scattering in great detail for collision between two CO molecules. Using advanced imaging methods and quasi-classical and fully quantum theory, we found that a synchronous movement can occur during CO-CO collisions, whereby a bump is followed by a move similar to a "do-si-do" in square dancing. This resulted in little angular deflection but high RET to both partners, a very unusual combination. The associated conditions suggest that this process can occur in other molecule-molecule systems.

Imaging inelastic scattering of CO with argon: polarization dependent differential cross sections.

Rotationally inelastic scattering of carbon monoxide (CO) with Argon at a collision energy of 700 cm-1 has been investigated by measuring polarization dependent differential scattering cross sections (PDDCSs) for rotationally excited CO molecules using a crossed molecular beam apparatus coupled with velocity-map ion imaging. A simple and robust (1 + 1' + 1'') VUV (Vacuum Ultra-Violet) REMPI (Resonance Enhanced Multi Photon Ionization) scheme is used and images are obtained by setting the VUV light polarization direction parallel or perpendicular to the scattering plane. Clear differences between the images for the two polarizations are observed, indicating strong collision induced alignment of the rotational angular momentum of scattered CO. A direct image analysis procedure as described in our previously published paper (A. G. Suits et al., J. Phys. Chem. A., 2015, 119, 5925), is employed to extract the fully quantum state resolved alignment-free differential cross sections (DCSs) and the state-to-state angle-dependent alignment moments for each final rotational state. The experimental results are compared with advanced theory, in particular with the predictions of CC QM (Close-Coupling Quantum Mechanical) and QCT (Quasi-Classical Trajectory) calculations. The agreement between experiment and theory is generally found to be quite good throughout the entire scattering angle range for all the final states probed, showing the reliability of the experiment and use of the direct extraction method, as well as the accuracy of the potential surface over the studied collision energy range. A classical kinematic apse (hard shell) model was found to be useful in interpreting the measured collision induced alignment moments.

Molecular Dynamics Study of the Photodesorption of CO Ice.

Photodesorption of CO ice is suggested to be the main process that maintains a measurable amount of gaseous CO in cold interstellar clouds. A classical molecular dynamics simulation is used to gain insight into the underlying mechanism. Site-site pair potentials were developed on the basis of ab initio calculations for the ground and excited nonrigid CO dimer. Both amorphous and crystalline CO clusters were created and characterized by their densities, expansion coefficients, binding energies, specific heats, and radial distribution functions. Selected CO molecules were electronically excited with 8.7-9.5 eV photons. CO returns to the ground state after a finite lifetime on the excited potential surface. Two desorption mechanisms are found: (1) direct desorption where excited CO itself is released from the cluster after landing on the ground state in an unfavorable orientation; (2) "kick-out" desorption where excited CO kicks out a neighboring CO molecule. These findings are in accord with laboratory experiments. Little dependence on size of the cluster, excitation energy and temperature in the 6-18 K range was found. The predicted photodesorption probability is 4.0 × 10(-3) molecules photon(-1), smaller by a factor of 3-11 than that given by experiments.

Line strengths of rovibrational and rotational transitions within the X³Σ⁻ ground state of NH.

A new line list for rovibrational and rotational transitions, including fine structure, within the NH X³Σ⁻ ground state has been created. It contains line intensities in the form of Einstein A and f-values, for all possible bands up to v' = 6, and for J up to between 25 and 44. The intensities are based on a new dipole moment function (DMF), which has been calculated using the internally contracted multi-reference configuration interaction method with an aug-cc-pV6Z basis set. The programs RKR1, LEVEL, and PGOPHER were used to calculate line positions and intensities using the most recent spectroscopic line position observations and the new DMF, including the rotational dependence on the matrix elements. The Hund's case (b) matrix elements from the LEVEL output (available as Supplement 1 of the supplementary material) have been transformed to the case (a) form required by PGOPHER. New relative intensities for the (1,0) band have been measured, and the calculated and observed Herman-Wallis effects are compared, showing good agreement. The line list (see Supplement 5 of the supplementary material) will be useful for the study of NH in astronomy, cold and ultracold molecular systems, and in the nitrogen chemistry of combustion.

Ab Initio Molecular Dynamics Calculations versus Quantum-State-Resolved Experiments on CHD3 + Pt(111): New Insights into a Prototypical Gas-Surface Reaction.

The dissociative chemisorption of methane on metal surfaces is of fundamental and practical interest, being a rate-limiting step in the steam reforming process. The reaction is best modeled with quantum dynamics calculations, but these are currently not guaranteed to produce accurate results because they rely on potential energy surfaces based on untested density functionals and on untested dynamical approximations. To help overcome these limitations, here we present for the first time statistically accurate reaction probabilities obtained with ab initio molecular dynamics (AIMD) for a polyatomic gas-phase molecule reacting with a metal surface. Using a general purpose density functional, the AIMD reaction probabilities are in semiquantitative agreement with new quantum-state-resolved experiments on CHD3 + Pt(111). The comparison suggests the use of the sudden approximation for treating the rotations even though CHD3 has large rotational constants and yields an estimated reaction barrier of 0.9 eV for CH4 + Pt(111).

Effects of reagent rotation and vibration on H + OH (υ, j)→ O + H2.

The dynamics of the reaction H + OH → O ((3)P) + H2 have been studied in a series of quasi-classical trajectory (QCT) calculations and transition state theory (TST) methods using high quality (3)A' and (3)A″ potential energy surfaces (PESs). Accurate OH (υ, j) state resolved cross sections and rate constants on both potential energy surfaces are presented and fitted for OH at (υ = 0, j = 0-16) and (υ = 1, j = 0-6). The cross sections were calculated for different collisional energies (Ec), ranging from the threshold energy at each specific rovibrational state up to 1.0 eV with step sizes of 0.1 eV or less. They increase steeply with collision energy when the barrier to reaction can be overcome, after which the cross sections stay nearly constant with energy. State resolved rate constants in the temperature range 200-2500 K are presented based on the cross sections. Total thermal rate constants were calculated by summing the rates for reaction on the (3)A' and (3)A″ potential energy surfaces weighted by 1/3 and taking into account the thermal populations of the rovibrational states of the OH molecules. The currently calculated thermal rate constants generally agree well with previous indirectly obtained rate constants by Tsang et al. (Tsang, W.; Hampson, R. F. Chemical Kinetic Data Base for Combustion Chemistry. Part I. Methane and Related Compounds. J. Phys. Chem. Ref. Data 1986, 15, 1087-1279). It is shown that the improved canonical variational transition (CVT) treatments with the approximation of zero-curvature tunneling (ZCT) or small-curvature tunneling (SCT) produce results more in accord with the QCT results than the TST and CVT methods. The reactions are governed by the direct reaction mechanism. The rate constants for OH in excited vibrational and rotational states are orders of magnitude larger than the thermal rate constants, which needs to be taken into account in astrochemical models.

The resonance Raman spectra of spheroidene revisited with a first-principles approach.

The resonance Raman (RR) spectra of different configurations of spheroidene are calculated by means of quantum chemical methods to investigate the nature of the cis configuration of this carotenoid molecule in the photosynthetic reaction center (RC) of the purple bacterium Rhodobacter sphaeroides. For validation of our methodology, we also calculate the spectrum of the all-trans structure present in the light-harvesting complexes of this bacterium. While former theoretical resonance Raman studies only considered truncated models of spheroidene, we report on calculations employing the full pigment here. The calculated frequencies for the all-trans configuration are in good agreement with former experimental and simulated data. Among the possible cis structures, the 15,15'-cis configuration shows a RR spectrum that is in best agreement with the experimental spectrum of spheroidene in the RC. In order to assess model truncation effects, we compare calculations for the full spheroidene molecule to those for the truncated model. While the main features can already be found in the latter, the full model leads to considerably different intensities in the region around 1150 cm(-1), which improve the agreement with experiment. A slight mismatch for the vibrational frequencies in the C=C stretch region is investigated by considering a model for spheroidene in the binding pocket comprising more than 500 atoms in total. The results do not lead to improved agreement with experiment, in contrast to the simpler strategy of introducing constraints in the structural optimization of a truncated spheroidene model. The calculated RR spectrum of the 13,14-cis configuration shows additional features which can also be identified in the experimental RR spectrum. This shows that the most likely cis structure is the 15,15'-cis configuration. Besides this, the 13,14-cis configuration remains a candidate for an additional spheroidene structure in the RC of Rhodobacter sphaeroides mutant R26.

Configuration of spheroidene in the photosynthetic reaction center of Rhodobacter sphaeroides : a comparison of wild-type and reconstituted R26.

We compare the resonance Raman spectra acquired at two excitation wavelengths, 496.5 and 514.5 nm, of spheroidene in the wild-type reaction center of Rhodobacter sphaeroides and reconstituted into the reaction center of the Rhodobacter sphaeroides mutant R26. Our earlier work showed that the reconstituted R26 reaction center holds spheroidene in two configurations: 15,15'-cis and another configuration. Here we show that in the wild-type reaction center only 15,15'-cis spheroidene is present. In the resonance Raman spectra of the reconstituted R26 reaction centers, a transition is identified that arises exclusively from the second configuration. According to density-functional-theory calculations, this transition is specific for the 13,14-cis configuration.

Quantum mechanical calculations for the H2O + hnu --> O(1D) + H2 photodissociation process.

Quantum mechanical wavepacket calculations for the photodissociation of water in the second absorption band are presented. Using O + H2 Jacobi coordinates, partial cross sections for the O(1D) + H2 channel are calculated for different initial rotational states. Conical intersection and Renner-Teller effects are included. The branching ratios for the four accessible dissociation channels at 121.6 nm are in good agreement with experiment (J. Chem. Phys. 1982, 77, 2432). The calculations predict significant rotational and vibrational excitation of the H2 fragments. Photodissociation of ortho and para water produces predominantly, but not exclusively, ortho and para H2 fragments, respectively.

Photoprocesses in protoplanetary disks.

Circumstellar disks are exposed to intense ultraviolet (UV) radiation from the young star. In the inner disks, the UV radiation can be enhanced by more than seven orders of magnitude compared with the average interstellar radiation field, resulting in a physical and chemical structure that resembles that of a dense photon-dominated region (PDR). This intense UV field affects the chemistry, the vertical structure of the disk, and the gas temperature, especially in the surface layers. The parameters which make disks different from more traditional PDRs are discussed, including the shape of the UV radiation field, grain growth, the absence of PAHs, the gas/dust ratio and the presence of inner holes. Illustrative infrared spectra from the Spitzer Space Telescope are shown. New photodissociation cross sections for selected species, including simple ions, are presented. Also, a summary of cross sections at the Lyman alpha 1216 A line, known to be strong for some T Tauri stars, is made. Photodissociation and ionization rates are computed for different radiation fields with color temperatures ranging from 30000 to 4000 K and grain sizes up to a few microm. The importance of a proper treatment of the photoprocesses is illustrated for the transitional disk toward HD 141569A which includes grain growth.

Photodissociation of the water dimer: three-dimensional quantum dynamics studies on diabatic potential-energy surfaces.

The results are presented of three-dimensional model studies of the photodissociation of the water dimer following excitation in the first absorption band. Diabatic potential-energy surfaces are used to investigate the photodissociation following excitation of the hydrogen bond donor molecule and of the hydrogen bond acceptor molecule. In both cases, the degrees of freedom considered are the two OH-stretch modes of the molecule being excited, and the dimer stretch vibration. The diabatic potentials are based on adiabatic potential surfaces computed with the multireference configuration-interaction method, and the dynamics of dissociation was studied using the time-dependent wave-packet method. The dynamics calculations yield a donor spectrum extending over roughly the same range of frequencies as the spectrum of the water monomer computed at the same level of theory. The acceptor spectrum has the same width as the monomer spectrum, but is shifted to the blue by 0.4-0.5 eV. The dimer spectrum obtained by averaging the donor and the acceptor spectrum is broader than the monomer spectrum, with the center of the dimer first absorption band shifted to the blue by about 0.2 eV relative to the monomer band. Our reduced dimensionality calculations do not find the red tail predicted for the dimer first absorption band by Harvey et al. [J. Chem. Phys. 109, 8747 (1998)]. This conclusion also holds if preexcitation of the dimer stretch vibration with one or two quanta is considered.

Quantitative spectroscopic and theoretical study of the optical absorption spectra of H2O, HOD, and D2O in the 125-145 nm region.

The room temperature absorption spectra of water and its isotopomers D2O and HOD have been determined in absolute cross section units in the 125 to 145 nm wavelength region using synchrotron radiation. The experimental results for these B band spectra are compared with results from quantum mechanical calculations using accurate diabatic ab initio potentials. A Monte Carlo sampling over the initial rotational states of the molecules is applied in order to calculate the cross sections at a temperature of 300 K. The overall rotation of the water molecule is treated exactly. Both for the experimental and for the theoretical spectrum an analysis is made in terms of a component attributed to rapid direct dissociation processes and a component attributed to longer-lived resonances. The agreement between the results from experiment and theory is excellent for H2O and D2O. In the case of HOD in the results of theory two more resonances are found at low energy. It is demonstrated that the width of the resonances of 0.04 eV is the result of overlapping and somewhat narrower resonances in the spectra of molecules differing in rotational ground state.

Photodissociation of the phosphine-substituted transition metal carbonyl complexes Cr(CO)(5)L and Fe(CO)(4)L: a theoretical study.

The photochemistry of the phosphine-substituted transition metal carbonyl complexes Cr(CO)(5)PH(3) and ax-Fe(CO)(4)PH(3) is studied with time-dependent DFT theory to explore the propensity of the excited molecules to expel their ligands. The influence of the PH(3) ligand on the properties of these complexes is compared with the photodissociation behavior of the binary carbonyl complexes Cr(CO)(6) and Fe(CO)(5). The lowest excited states of Cr(CO)(5)PH(3) are metal-to-ligand charge transfer (MLCT) states, of which the first three are repulsive for PH(3) but modestly bonding for the axial and equatorial CO ligands. The repulsive nature is due to mixing of the initial MLCT state with a ligand field (LF) state. A barrier is encountered along the dissociation coordinate if the avoided crossing between these states occurs beyond the equilibrium distance. This is the case for expulsion of CO but not for the PH(3) group as the avoided state crossing occurs within the equilibrium Cr-P distance. The lowest excited state of ax-Fe(CO)(4)PH(3) is a LF state that is repulsive for both PH(3) and the axial CO. Excited-state quantum dynamics calculations for this state show a branching ratio of 99 to 1 for expulsion of the axial phosphine ligand over an axial CO ligand. The nature of the phosphorus ligand in these Cr and Fe complexes is only of modest importance. Complexes containing the three-membered phosphirane or unsaturated phosphirene rings have dissociation curves for their lowest excited states that are similar to those having a PH(3) ligand. Analysis of their ground-state Cr-P bond properties in conjunction with frontier orbital arguments indicate these small heterocyclic groups to differ from the PH(3) group mainly by their enhanced sigma-donating ability. All calculations indicate that the excited Cr(CO)(5)L and Fe(CO)(4)L molecules (L = PH(3), PC(2)H(5), and PC(2)H(3)) prefer dissociation of their phosphorus substituent over that of an CO ligand. This suggests that the photochemical approach may be a viable complement to the ligand exchange and redox methods that are currently employed to demetalate transition metal complexed organophosphorus compounds.