RT info:eu-repo/semantics/article
T1 Structure and Spectroscopic Insights for CH3PCO Isomers: A High-Level Quantum Chemical Study
A1 Sanz Novo, Miguel
A1 Redondo Cristóbal, María del Pilar
A1 Sánchez, Clara Isabel
A1 Largo Cabrerizo, Antonio
A1 Barrientos Benito, María Carmen
A1 Sordo, José Ángel
K1 Química cuántica
K1 Isomería molecular
K1 Espectroscopía teórica
K1 2307 Química Física
K1 2212 Física Teórica
AB The exploration of phosphorus-bearing species stands as a prolific field in current astrochemical research, particularly within the context of prebiotic chemistry. Herein, we have employed high-level quantum chemistry methodologies to predict the structure and spectroscopic properties of isomers composed of a methyl group and three P, C, and O atoms. We have computed relative and dissociation energies, as well as rotational, rovibrational, and torsional parameters using the B2PLYPD3 functional and the explicitly correlated coupled cluster CCSD(T)-F12b method. Based upon our study, all the isomers exhibit a bent heavy atom skeleton with CH3PCO being the most stable structure, regardless of the level theory employed. Following in energy, we found four high-energy isomers, namely, CH3OCP, CH3CPO, CH3COP, and CH3OPC. The computed adiabatic dissociation energies support the stability of all [CH3, P, C, O] isomers against fragmentation into CH3 and [P, C, O]. Torsional barrier heights associated with the methyl internal rotation for each structure have been computed to evaluate the occurrence of possible A−E splittings in the rotational spectra. For the most stable isomer, CH3PCO, we found a V3 barrier of 82 cm−1, which is slightly larger than that obtained experimentally for the N-counterpart, CH3NCO, yet still very low. Therefore, the analysis of its rotational spectrum can be anticipated as a challenging task owing to the effect of the CH3 internal rotation. The complete set of spectroscopic constants and transition frequencies reported here for the most stable isomer, CH3PCO, is intended to facilitate eventual laboratory searches.
SN 1089-5639
YR 2024
FD 2024
LK https://uvadoc.uva.es/handle/10324/80093
UL https://uvadoc.uva.es/handle/10324/80093
LA eng
NO The Journal of Physical Chemistry A, 2024, 128, 20, 4083-4091
NO Producción Científica
DS UVaDOC
RD 14-mar-2026