Dataset Information

Isomerization and Fragmentation Reactions on the [C₂SH₄] Potential Energy Surface: The Metastable Thione S-Methylide Isomer.

ABSTRACT: Thione S-methylide, parent species of the thiocarbonyl ylide family, is a 1,3-dipolar species on the [C₂SH₄] potential energy surface, not so much studied as its isomers, thiirane, vinyl thiol, and thioacetaldehyde. The conrotatory ring-closure reaction toward thiirane was studied in the 90s, but no complete analysis of the potential energy surface is available. In this paper, we report a computational study of the reaction scheme linking all species. We employed several computational methods (density functional theory, CCSD(T) composite schemes, and CASSCF/CASPT2 multireference procedures) to find the best description of thione S-methylide, its isomers, and transition states. The barrier from thiirane to thione S-methylide amounts to 52.2 kcal mol^-1 (against 17.6 kcal mol^-1 for the direct one), explaining why thiocarbonyl ylides cannot be prepared from thiiranes. Conversion of thiirane to vinyl thiol implies a large barrier, supporting why the reaction has been observed only at high temperatures. Fragmentations of thiirane to S(³P) or S(¹D) and ethylene as well as decomposition to hydrogen sulfide plus acetylene were also explored. Triplet and singlet open-shell species were identified as intermediates in the fragmentations, with energies lower than the transition state between thiirane and vinyl thiol, explaining the preference of the latter at low temperatures.

SUBMITTER: Salta Z

PROVIDER: S-EPMC8023414 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Similar Datasets

Project description:This computational study investigates the adsorption of various spiropyran and merocyanine isomers on a NaCl substrate using a combination of density functional theory (DFT) and molecular mechanics (MM) calculations. Four different charge methods were used to determine the partial atomic charges for the adsorbate molecules, including Mulliken population analysis and three electrostatic potential (ESP) methods (Merz-Kollman, ChelpG, and Hu-Lu-Yang), while three different force fields (AMBER 3, CHARMM 27, and MM+) were employed for the MM calculations. The results show that the various DFT charge methods produced similar outcomes for the molecules' partial atomic charges, with some exceptions for individual atoms and methods. Additionally, it was found that the ESP charge methods were more sensitive to the conformer orientation than the Mulliken approach. The adsorption behavior of merocyanine conformers with the central bond in trans orientation (T-conformers) was similar for various configurations, with the molecule adsorbing mostly flat with its aromatic rings almost parallel to the substrate. However, C-conformers (with their central bond in cis orientation) and spiropyran isomers exhibited inconsistent adsorption behavior, mostly because only some of the aromatic rings contributed to the adsorption behavior. Due to additional van der Waals interactions of more aromatic rings, the adsorption energies for T-conformers are consistently 0.2-0.3 eV higher than for C-conformers and for spiropyran. The study found that the adsorption geometries and energies of stable T-conformers were independent of the partial atomic charge scheme and force field used, and C-conformers show parameter-dependent behavior upon adsorption, leading to metastable configurations. These findings indicate viable pathways during the spiropyran-merocyanine isomerization reactions. Therefore, the results provide initial insights into the possibility of switching spiropyran isomers into merocyanine isomers and vice versa after adsorption onto substrates.

Dataset Information

Isomerization and Fragmentation Reactions on the [C₂SH₄] Potential Energy Surface: The Metastable Thione S-Methylide Isomer.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Dataset Information

Isomerization and Fragmentation Reactions on the [C2SH4] Potential Energy Surface: The Metastable Thione S-Methylide Isomer.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Isomerization and Fragmentation Reactions on the [C₂SH₄] Potential Energy Surface: The Metastable Thione S-Methylide Isomer.