Quantal treatment of O2--Ar vibrational relaxation at hypersonic temperatures

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/143097/1/6.2017-0661.pd

The furan microsolvation blind challenge for quantum chemical methods: First steps

© 2018 Author(s). Herein we present the results of a blind challenge to quantum chemical methods in the calculation of dimerization preferences in the low temperature gas phase. The target of study was the first step of the microsolvation of furan, 2-methylfuran and 2,5-dimethylfuran with methanol. The dimers were investigated through IR spectroscopy of a supersonic jet expansion. From the measured bands, it was possible to identify a persistent hydrogen bonding OH-O motif in the predominant species. From the presence of another band, which can be attributed to an OH-π interaction, we were able to assert that the energy gap between the two types of dimers should be less than or close to 1 kJ/mol across the series. These values served as a first evaluation ruler for the 12 entries featured in the challenge. A tentative stricter evaluation of the challenge results is also carried out, combining theoretical and experimental results in order to define a smaller error bar. The process was carried out in a double-blind fashion, with both theory and experimental groups unaware of the results on the other side, with the exception of the 2,5-dimethylfuran system which was featured in an earlier publication

The first microsolvation step for furans : new experiments and benchmarking strategies

The site-specific first microsolvation step of furan and some of its derivatives with methanol is explored to benchmark the ability of quantum-chemical methods to describe the structure, energetics, and vibrational spectrum at low temperature. Infrared and microwave spectra in supersonic jet expansions are used to quantify the docking preference and some relevant quantum states of the model complexes. Microwave spectroscopy strictly rules out in-plane docking of methanol as opposed to the top coordination of the aromatic ring. Contrasting comparison strategies, which emphasize either the experimental or the theoretical input, are explored. Within the harmonic approximation, only a few composite computational approaches are able to achieve a satisfactory performance. Deuteration experiments suggest that the harmonic treatment itself is largely justified for the zero-point energy, likely and by design due to the systematic cancellation of important anharmonic contributions between the docking variants. Therefore, discrepancies between experiment and theory for the isomer abundance are tentatively assigned to electronic structure deficiencies, but uncertainties remain on the nuclear dynamics side. Attempts to include anharmonic contributions indicate that for systems of this size, a uniform treatment of anharmonicity with systematically improved performance is not yet in sight

Theoretical Studies of Two Key Low-Lying Carbenes of C5H2 Missing in the Laboratory

The equilibrium geometries and spectroscopic properties of two key singlet carbenes, buta-1,3-diynylcarbene (6) and 2-methylenebicyclo[1.1.0]but-1(3)-en-4-ylidene (9), which have not been experimentally observed to date, are investigated using high-level coupled-cluster (CC) methods. The current theoretical study necessitates new experimental data on C5H2 isomers considering the relevance of these molecules to interstellar chemistry. Bent-pentadiynylidene (4) has been missing in the laboratory and the prime focus of our earlier theoretical work. The present theoretical study indicates that isomers 6 and 9 are also viable experimental targets. Apart from ethynylcyclopropenylidene (2), pentatetraenylidene (3), ethynylpropadienylidene (5), and 3-(didehydrovinylidene)cyclopropene (8), which are identified by Fourier transform microwave spectroscopy, the dipole moments of elusive 4, 6, and 9 are also nonzero (μ ≠ 0). The relative energies of these isomers, calculated at the CCSDT(Q)/CBS level of theory, with respect to linear triplet pentadiynylidene (1) reveal that they all lie within 25.1 kcal mol-1. Therefore, geometric, energetic, aromatic, and spectroscopic parameters are reported here, which may assist the efforts of molecular spectroscopists in the future. Anharmonic vibrational calculations on isomers 6 and 9 indicate that the former is loosely bound and would be challenging to be detected experimentally. Among the undetected carbenes, 9 may be considered as a potential target molecule considering its higher polarity and aromatic nature