1. Accurate structural and spectroscopic characterization of prebiotic molecules: The neutral and cationic acetyl cyanide and their related species
- Author
-
Cristina Puzzarini, Majdi Hochlaf, A. Bellili, Roberto Linguerri, Laboratoire de Modélisation et Simulation Multi Echelle (MSME), Université Paris-Est Marne-la-Vallée (UPEM)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Université Paris-Est Marne-la-Vallée (UPEM), Bellili, A., Linguerri, R., Hochlaf, M., Puzzarini, C, and Linguerri, Roberto
- Subjects
TORSION-VIBRATION INTERACTION ,Extrapolation ,General Physics and Astronomy ,Acetyl cyanide ,ROTATIONAL SPECTROSCOPY ,Ion ,MICROWAVE-SPECTRUM ,chemistry.chemical_compound ,Physics and Astronomy (all) ,Computational chemistry ,Ionization ,[CHIM] Chemical Sciences ,EQUILIBRIUM STRUCTURE ,WAVE-FUNCTIONS ,Molecule ,[CHIM]Chemical Sciences ,Physical and Theoretical Chemistry ,ComputingMilieux_MISCELLANEOUS ,AB-INITIO ,GAUSSIAN-BASIS SETS ,ANHARMONIC-FORCE FIELDS ,INTERSTELLAR-MOLECULES ,Characterization (materials science) ,Bond length ,[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry ,[CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry ,chemistry ,Excited state ,COUPLED-CLUSTER THEORY - Abstract
In an effort to provide an accurate structural and spectroscopic characterization of acetyl cyanide, its two enolic isomers and the corresponding cationic species, state-of-the-art computational methods, and approaches have been employed. The coupled-cluster theory including single and double excitations together with a perturbative treatment of triples has been used as starting point in composite schemes accounting for extrapolation to the complete basis-set limit as well as core-valence correlation effects to determine highly accurate molecular structures, fundamental vibrational frequencies, and rotational parameters. The available experimental data for acetyl cyanide allowed us to assess the reliability of our computations: structural, energetic, and spectroscopic properties have been obtained with an overall accuracy of about, or better than, 0.001 Å, 2 kcal/mol, 1-10 MHz, and 11 cm(-1) for bond distances, adiabatic ionization potentials, rotational constants, and fundamental vibrational frequencies, respectively. We are therefore confident that the highly accurate spectroscopic data provided herein can be useful for guiding future experimental investigations and/or astronomical observations.
- Published
- 2015