Dataset Information

State-resolved studies of CO₂ sticking to CO₂ ice.

ABSTRACT: Internal vibrations may affect the adsorption, scattering, and reactions of molecules impinging onto a surface. The energy of the ν ₃ antisymmetric stretch vibration of CO₂ slightly exceeds the desorption energy of CO₂ bound to CO₂ ice. We use supersonic molecular beam techniques and rovibrationally state-resolved excitation to determine whether this vibration affects condensation of gas phase CO₂ to its ice. We detect sticking and CO₂ ice formation using RAIRS and quantify the sticking probability using the King and Wells method with modulation of the vibrational excitation and Fourier transform based detection. We find that the influence of this vibration on the structure of the formed ice and on the sticking probability is negligible under our conditions. Based on our detection limit, we quantify the weighted average sticking probability at approximately 0.9 and the difference between the state-resolved and weighted average sticking probability as below 0.03%.

SUBMITTER: Jansen C

PROVIDER: S-EPMC10483124 | biostudies-literature | 2023

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

State-resolved studies of CO2 sticking to CO2 ice.

Jansen Charlotte C Juurlink Ludo B F LBF

Frontiers in chemistry 20230824

Internal vibrations may affect the adsorption, scattering, and reactions of molecules impinging onto a surface. The energy of the ν 3 antisymmetric stretch vibration of CO2 slightly exceeds the desorption energy of CO2 bound to CO2 ice. We use supersonic molecular beam techniques and rovibrationally state-resolved excitation to determine whether this vibration affects condensation of gas phase CO2 to its ice. We detect sticking and CO ...[more]

PMID: 37693167

Similar Datasets

Project description:We report a study of the photocatalytic reduction of CO2 to CO by zinc porphyrins covalently linked to [ReI(2,2'-bipyridine)(CO)3L]+/0 moieties with visible light of wavelength >520 nm. Dyad 1 contains an amide C6H4NHC(O) link from porphyrin to bipyridine (Bpy), Dyad 2 contains an additional methoxybenzamide within the bridge C6H4NHC(O)C6H3(OMe)NHC(O), while Dyad 3 has a saturated bridge C6H4NHC(O)CH2; each dyad is studied with either L = Br or 3-picoline. The syntheses, spectroscopic characterisation and cyclic voltammetry of Dyad 3 Br and [Dyad 3 pic]OTf are described. The photocatalytic performance of [Dyad 3 pic]OTf in DMF/triethanolamine (5 : 1) is approximately an order of magnitude better than [Dyad 1 pic]PF6 or [Dyad 2 pic]OTf in turnover frequency and turnover number, reaching a turnover number of 360. The performance of the dyads with Re-Br units is very similar to that of the dyads with [Re-pic]+ units in spite of the adverse free energy of electron transfer. The dyads undergo reactions during photocatalysis: hydrogenation of the porphyrin to form chlorin and isobacteriochlorin units is detected by visible absorption spectroscopy, while IR spectroscopy reveals replacement of the axial ligand by a triethanolaminato group and insertion of CO2 into the latter to form a carbonate. Time-resolved IR spectra of [Dyad 2 pic]OTf and [Dyad 3 pic]OTf (560 nm excitation in CH2Cl2) demonstrated electron transfer from porphyrin to Re(Bpy) units resulting in a shift of ν(CO) bands to low wavenumbers. The rise time of the charge-separated species for [Dyad 3 pic]OTf is longest at 8 (±1) ps and its lifetime is also the longest at 320 (±15) ps. The TRIR spectra of Dyad 1 Br and Dyad 2 Br are quite different showing a mixture of 3MLCT, IL and charge-separated excited states. In the case of Dyad 3 Br, the charge-separated state is absent altogether. The TRIR spectra emphasize the very different excited states of the bromide complexes and the picoline complexes. Thus, the similarity of the photocatalytic data for bromide and picoline dyads suggests that they share common intermediates. Most likely, these involve hydrogenation of the porphyrin and substitution of the axial ligand at rhenium.

Dataset Information

State-resolved studies of CO₂ sticking to CO₂ ice.

Publications

State-resolved studies of CO<sub>2</sub> sticking to CO<sub>2</sub> ice.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets