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1. Rotational state-to-state transition rate coefficients for H ₂ O + H ₂ O collisions at nonequilibrium conditions

   https://doi.org/10.1051/0004-6361/202450738  

   Mandal, Bikramaditya; Zoltowski, Michal; Cordiner, Martin; Lique, Francois; Babikov, Dmitri (August 2024, Astronomy & Astrophysics)

   Aims.The goal is to develop a database of rate coefficients for rotational state-to-state transitions in H₂O + H₂O collisions that is suitable for the modeling of energy transfer in nonequilibrium conditions, in which the distribution of rotational states of H₂O deviates from local thermodynamic equilibrium. Methods.A two-temperature model was employed that assumed that although there is no equilibrium between all possible degrees of freedom in the system, the translational and rotational degrees of freedom can be expected to achieve their own equilibria independently, and that they can be approximately characterized by Boltzmann distributions at two different temperatures,T_kinandT_rot. Results.Upon introducing our new parameterization of the collisional rates, taking into account their dependence on bothT_kinandT_rot, we find a change of up to 20% in the H₂O rotational level populations for both ortho and para-H₂O for the part of the cometary coma where the nonequilibrium regime occurs. 

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2. Experimental study of the proton-transfer reaction C + H ₂ ⁺ → CH ⁺ + H and its isotopic variant (D ₂ ⁺ )

   https://doi.org/10.1039/D0CP04810K  

   Hillenbrand, Pierre-Michel; Bowen, Kyle P.; Dayou, Fabrice; Miller, Kenneth A.; de Ruette, Nathalie; Urbain, Xavier; Savin, Daniel W. (December 2020, Physical Chemistry Chemical Physics)

   We report absolute integral cross section (ICS) measurements using a dual-source merged-fast-beams apparatus to study the titular reactions over the relative translational energy range of E r ∼ 0.01–10 eV. We used photodetachment of C − to produce a pure beam of atomic C in the ground electronic 3 P term, with statistically populated fine-structure levels. The H 2 + and D 2 + were formed in an electron impact ionization source, with well known vibrational and rotational distributions. The experimental work is complemented by a theoretical study of the CH 2 + electronic system in the reactant and product channels, which helps to clarify the possible reaction mechanisms underlying the ICS measurements. Our measurements provide evidence that the reactions are barrierless and exoergic. They also indicate the apparent absence of an intermolecular isotope effect, to within the total experimental uncertainties. Capture models, taking into account either the charge-induced dipole interaction potential or the combined charge-quadrupole and charge-induced dipole interaction potentials, produce reaction cross sections that lie a factor of ∼4 above the experimental results. Based on our theoretical study, we hypothesize that the reaction is most likely to proceed adiabatically through the 1 4 A′ and 1 4 A′′ states of CH 2 + via the reaction C( 3 P) + H 2 + ( 2 Σ+g) → CH + ( 3 Π) + H( 2 S). We also hypothesize that at low collision energies only H 2 + ( v ≤ 2) and D 2 + ( v ≤ 3) contribute to the titular reactions, due to the onset of dissociative charge transfer for higher vibrational v levels. Incorporating these assumptions into the capture models brings them into better agreement with the experimental results. Still, for energies ≲0.1 eV where capture models are most relevant, the modified charge-induced dipole model yields reaction cross sections with an incorrect energy dependence and lying ∼10% below the experimental results. The capture cross section obtained from the combined charge-quadrupole and charge-induced dipole model better matches the measured energy dependence but lies ∼30–50% above the experimental results. These findings provide important guidance for future quasiclassical trajectory and quantum mechanical treatments of this reaction. 

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3. The non-covalently bound SO⋯H ₂ O system, including an interpretation of the differences between SO⋯H ₂ O and O ₂ ⋯H ₂ O

   https://doi.org/10.1039/C8CP05749D  

   Misiewicz, Jonathon P.; Noonan, Julia A.; Turney, Justin M.; Schaefer, Henry F. (November 2018, Physical Chemistry Chemical Physics)

   Despite the interest in sulfur monoxide (SO) among astrochemists, spectroscopists, inorganic chemists, and organic chemists, its interaction with water remains largely unexplored. We report the first high level theoretical geometries for the two minimum energy complexes formed by sulfur monoxide and water, and we report energies using basis sets as large as aug-cc-pV(Q+d)Z and correlation effects through perturbative quadruple excitations. One structure of SO⋯H 2 O is hydrogen bonded and the other chalcogen bonded. The hydrogen bonded complex has an electronic energy of −2.71 kcal mol −1 and a zero kelvin enthalpy of −1.67 kcal mol −1 , while the chalcogen bonded complex has an electronic energy of −2.64 kcal mol −1 and a zero kelvin enthalpy of −2.00 kcal mol −1 . We also report the transition state between the two structures, which lies below the SO⋯H 2 O dissociation limit, with an electronic energy of −1.26 kcal mol −1 and an enthalpy of −0.81 kcal mol −1 . These features are much sharper than for the isovalent complex of O 2 and H 2 O, which only possesses one weakly bound minimum, so we further analyze the structures with open-shell SAPT0. We find that the interactions between O 2 and H 2 O are uniformly weak, but the SO⋯H 2 O complex surface is governed by the superior polarity and polarizability of SO, as well as the diffuse electron density provided by sulfur's extra valence shell. 

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4. Insights into the charge-transfer character of electronic transitions in ^R Cp ₂ Ti(C ₂ Fc) ₂ complexes using solvatochromism, resonance Raman spectroscopy, and TDDFT

   https://doi.org/10.1039/d0dt04282j  

   Carlton, Elizabeth S.; Sutton, Joshua J.; Gale, Ariel G.; Shields, George C.; Gordon, Keith C.; Wagenknecht, Paul S. (February 2021, Dalton Transactions)

   null (Ed.)

   A series of complexes with low-energy Fe II to Ti IV metal-to-metal charge-transfer (MMCT) transitions, Cp 2 Ti(C 2 Fc) 2 , Cp* 2 Ti(C 2 Fc) 2 , and MeOOC Cp 2 Ti(C 2 Fc) 2 , was investigated using solvatochromism and resonance Raman spectroscopy (RRS) augmented with time-dependent density functional theory (TDDFT) calculations in order to interrogate the nature of the CT transitions. Computational models were benchmarked against the experimental UV-Vis spectra and B3LYP/6-31G(d) was found to most faithfully represent the spectra. The energy of the MMCT transition was measured in 15 different solvents and a multivariate fit to the Catalán solvent parameters – solvent polarizability (SP), solvent dipolarity (SdP), solvent basicity (SB), and solvent acidity (SA) – was performed. The effect of SP indicates a greater degree of electron delocalization in the excited state (ES) than the ground state (GS). The small negative solvatochromism with respect to SdP indicates a smaller dipole moment in the ES than the GS. The effect of SB is consistent with charge-transfer to Ti. Upon excitation into the MMCT absorption band, the RRS data show enhancement of the alkyne stretching modes and of the out-of-plane bending modes of the cyclopentadienyl ring connected to Fe and the alkyne bridge. This is consistent with changes in the oxidation states of Ti and Fe, respectively. The higher-energy transitions (350–450 nm) show enhancement of vibrational modes consistent with ethnylcyclopentadienyl to Ti ligand-to-metal charge transfer (LMCT). The RRS data is consistent with the TDDFT predicted character of these transitions. TDDFT suggests that the lowest-energy transition in Cp 2 Ti(C 2 Fc) 2 CuI, where CuI is coordinated between the alkynes, retains its Fe II to Ti IV MMCT character, in agreement with the RRS data, but that the lowest-energy transitions have significant CuI to Ti character. For Cp 2 Ti(C 2 Fc) 2 CuI, excitation into the low-energy MMCT absorption band results in selective enhancement of the symmetric alkynyl stretching mode. 

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5. On comparison of luminescence properties of La ₂ Zr ₂ O ₇ and La ₂ Hf ₂ O ₇ nanoparticles

   https://doi.org/10.1111/jace.16693  

   Gupta, Santosh K.; Abdou, Maya; Ghosh, Partha S.; Zuniga, Jose P.; Manoharan, Ezhilarasan; Kim, HyeongJun; Mao, Yuanbing (July 2019, Journal of the American Ceramic Society)

   Abstract Unveiling the underlying mechanisms of properties of functional materials, including the luminescence differences among similar pyrochlores A₂B₂O₇, opens new gateways to select proper hosts for various optoelectronic applications by scientists and engineers. For example, although La₂Zr₂O₇(LZO) and La₂Hf₂O₇(LHO) pyrochlores have similar chemical compositional and crystallographic structural features, they demonstrate different luminescence properties both before and after doped with Eu³⁺ions. Based on our earlier work, LHO‐based nanophosphors display higher photo‐ and radioluminescence intensity, higher quantum efficiency, and longer excited state lifetime compared to LZO‐based nanophosphors. Moreover, under electronic O²⁻→Zr⁴⁺/Hf⁴⁺transition excitation at 306 nm, undoped LHO nanoparticles (NPs) have only violet blue emission, whereas LZO NPs show violet blue and red emissions. In this study, we have combined experimental and density functional theory (DFT) based theoretical calculation to explain the observed results. First, we calculated the density of state (DOS) based on DFT and studied the energetics of ionized oxygen vacancies in the band gaps of LZO and LHO theoretically, which explain their underlying luminescence difference. For Eu³⁺‐doped NPs, we performed emission intensity and lifetime calculations and found that the LHOE NPs have higher host to dopant energy transfer efficiency than the LZOE NPs (59.3% vs 24.6%), which accounts for the optical performance superiority of the former over the latter. Moreover, by corroborating our experimental data with the DFT calculations, we suggest that the Eu³⁺doping states in LHO present at exact energy position (both in majority and minority spin components) where oxygen defect states are located unlike those in LZO. Lastly, both the NPs show negligible photobleaching highlighting their potential for bioimaging applications. This current report provides a deeper understanding of the advantages of LHO over LZO as an advanced host for phosphors, scintillators, and fluoroimmunoassays. 

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