Candidate carriers and synthetic spectra of the 21- and 30-mu protoplanetary nebular bands

Computational chemistry is used here to determine the vibrational line spectrum of several candidate molecules. It is shown that the thiourea functional group, associated with various carbonaceous structures (mainly compact and linear aromatic clusters), is able to mimic the 21-$\mu$m band emitted by a number of proto-planetary nebulae. The combination of nitrogen and sulphur in thiourea is the essential source of emission in this model: the band disappears if these species are replaced by carbon. The astronomical 21-$\mu$m feature extends redward to merge with another prominent band peaking between 25 and 30 $\mu$m, also known as the 30-$\mu$m band. It is found that the latter can be modelled by the combined spectra of aliphatic chains, made of CH$_{2}$ groups, oxygen bridges and OH groups, which provide the 30-$\mu$m emission. The absence of oxygen all but extinguishes the 30-$\mu$m emission. The emission between the 21- and 30-$\mu$m bands is provided mainly by thiourea attached to linear aromatic clusters. The chemical software reveals that the essential role of the heteroatoms N, S and O stems from their large electronic charge. It also allows to determine the type of atomic vibration responsible for the different lines of each structure, which helps selecting the most relevant structures. A total of 22 structures have been selected here, but their list is far from being exhaustive; they are only intended as examples of 3 generic classes. When background dust emission is added, model spectra are obtained, which are able to satisfactorily reproduce recent observations of proto-planetary nebulae. The relative numbers of atomic species used in this model are typically H:C:O:N:S=53:36:8:2:1.Comment: 9 pages, 14 figure

Six-fold-symmetry internal rotation in toluenes: the low barrier challenge of 2,6-and 3,5-difluorotoluene

Pure six-fold symmetry (V6) internal rotation poses significant challenges to experimental and theoretical determination, as the very low torsional barriers result in huge tunneling splittings difficult to identify and to model. Here we resolved the methyl group internal rotation dynamics of 2,6- and 3,5-difluorotoluene using a newly developed computer code especially adapted to V6 problems. The jet-cooled rotational spectra of the title molecules in the 5–25 GHz region revealed internal rotation tunneling doublings of up to 3.6 GHz, which translated in methyl group potential barriers of V6 = 0.14872(24) and 0.0856(10) kJ mol−1, respectively, in the vibrational ground-state. Additional information on Stark effects and carbon isotopic species in natural abundance provided structural data and the electric dipole moments for both molecules. Ab initio calculations at the MP2 level do not reproduce the tiny torsional barriers, calling for experiments on other systems and additional theoretical models.DFGMINECO/CTQ2012-39132-C02-0

Precise dipole moments and quadrupole coupling constants of the cis and trans conformers of 3-aminophenol: Determination of the absolute conformation

The rotational constants and the nitrogen nuclear quadrupole coupling constants of cis-3-aminophenol and trans-3-aminophenol are determined using Fourier-transform microwave spectroscopy. We examine several $J=2\leftarrow{}1$ and $1\leftarrow{}0$ hyperfine-resolved rotational transitions for both conformers. The transitions are fit to a rigid rotor Hamiltonian including nuclear quadrupole coupling to account for the nitrogen nucleus. For cis-3-aminophenol we obtain rotational constants of A=3734.930 MHz, B=1823.2095 MHz, and C=1226.493 MHz, for trans-3-aminophenol of A=3730.1676 MHz, B=1828.25774 MHz, and C=1228.1948 MHz. The dipole moments are precisely determined using Stark effect measurements for several hyperfine transitions to $\mu_a=1.7735$ D, $\mu_b=1.5195$ D for cis-3-aminophenol and $\mu_a=0.5563$ D, $\mu_b=0.5376$ D for trans-3-aminophenol. Whereas the rotational constants and quadrupole coupling constants do not allow to determinate the absolute configuration of the two conformers, this assignment is straight-forward based on the dipole moments. High-level \emph{ab initio} calculations (B3LYP/6-31G^* to MP2/aug-cc-pVTZ) are performed providing error estimates of rotational constants and dipole moments obtained for large molecules by these theoretical methods.Comment: 9 pages, 4 tables, 3 figures (RevTeX

N-methyl inversion in pseudo-pelletierine

We have previously conducted rotational studies of several tropanes, \footnote {E.~J.~Cocinero, A.~Lesarri, P.~\'Ecija, J.-U.~Grabow, J.~A.~Fern\'andez, F.~Casta\~{n}o, \textit{Phys. Chem. Chem. Phys.} \textbf{2010}, \textit{49}, 4503}$^{,}$\footnote { P.~\'Ecija, E.~J.~Cocinero, A.~Lesarri, F. ~J. ~Basterretxea, J.~A.~Fern\'andez, F.~Casta\~{n}o, \textit{Chem. Phys. Chem.} \textbf{2013}, \textit{14}, 1830}$^{,}$\footnote { P.~\'Ecija, M. ~Vallejo-Lopez, I. ~Uriarte, F. ~J. ~Basterretxea, A. Lesarri, J.~A.~Fern\'andez, E.~J.~Cocinero, \textit{submitted} \textbf{2016}} since this bicyclic structural motif forms the core of different alkaloids of pharmaceutical interest. Now we report on the conformational properties and molecular structure of pseudo-pelletierine (9-methyl-9-azabicyclo[3.3.1]nonan-3-one), probed in a jet expansion with Fourier-transform microwave spectroscopy. Pseudo-pelletierine is an azabicycle with two fused six-membered rings, where the \textit{N}-methyl group can produce inverting axial o equatorial conformations. The two conformations were detected in the rotational spectrum, recorded in the region 6-18 GHz. Unlike tropinone and \textit{N}-methylpiperidone, where the most stable conformer is equatorial, the axial species was found dominant for pseudo-pelletierine. All monosubstituted isotopic species ($^{13}$C, $^{15}$N and $^{18}$O) were identified for the axial conformer, leading to an accurate determination of the effective and substitution structures. An estimation of conformational populations was derived from relative intensities. The experimental results will be compared with \textit{ab initio} (MP2) and DFT (M06-2X, B3LYP) calculations

The Structure of 2,6-Di-tert-butylphenol–Argon by Rotational Spectroscopy

The molecular structure of a van der Waals-bonded complex involving 2,6-di-tert-butylphenol and a single argon atom has been determined through rotational spectroscopy. The experimentally derived structural parameters were compared to the outcomes of quantum chemical calculations that can accurately account for dispersive interactions in the cluster. The findings revealed a π-bound configuration for the complex, with the argon atom engaging the aromatic ring. The microwave spectrum reveals both fine and hyperfine tunneling components. The main spectral doubling is evident as two distinct clusters of lines, with an approximate separation of 179 MHz, attributed to the torsional motion associated with the hydroxyl group. Additionally, each component of this doublet further splits into three components, each with separations measuring less than 1 MHz. Investigation into intramolecular dynamics using a one-dimensional flexible model suggests that the main tunneling phenomenon originates from equivalent positions of the hydroxyl group. A double-minimum potential function with a barrier of 1000 (100) cm−1 effectively describes this extensive amplitude motion. However, the three-fold fine structure, potentially linked to internal motions within the tert-butyl group, requires additional scrutiny for a comprehensive understanding

The structure of 2,6-di-tert-butylphenol–argon by rotational spectroscopy

Producción CientíficaThe molecular structure of a van der Waals-bonded complex involving 2,6-di-tert-butylphenol and a single argon atom has been determined through rotational spectroscopy. The experimentally derived structural parameters were compared to the outcomes of quantum chemical calculations that can accurately account for dispersive interactions in the cluster. The findings revealed a π-bound configuration for the complex, with the argon atom engaging the aromatic ring. The microwave spectrum reveals both fine and hyperfine tunneling components. The main spectral doubling is evident as two distinct clusters of lines, with an approximate separation of 179 MHz, attributed to the torsional motion associated with the hydroxyl group. Additionally, each component of this doublet further splits into three components, each with separations measuring less than 1 MHz. Investigation into intramolecular dynamics using a one-dimensional flexible model suggests that the main tunneling phenomenon originates from equivalent positions of the hydroxyl group. A double-minimum potential function with a barrier of 1000 (100) cm−1 effectively describes this extensive amplitude motion. However, the three-fold fine structure, potentially linked to internal motions within the tert-butyl group, requires additional scrutiny for a comprehensive understanding.Ministerio de Ciencia e Innovación y Fondo Europeo de Desarrollo Regional (FEDER) - (grant PID2021-125015NBI00)Junta de Castilla y León y Fondo Europeo de Desarrollo Regional (FEDER) - (grants INFRARED IR2020-1-UVa02 and INFRARED IR2021-UVa13

Adaptive Response to Solvation in Flexible Molecules: Oligo Hydrates of 4-Hydroxy-2-butanone

Structural changes induced by water play a pivotal role in chemistry and biology but remain challenging to predict, measure, and control at molecular level. Here we explore size-governed gas-phase water aggregation in the flexible molecule 4-hydroxy-2-butanone, modeling the conformational adaptability of flexible substrates to host water scaffolds and the preference for sequential droplet growth. The experiment was conducted using broadband rotational spectroscopy, rationalized with quantum chemical calculations. Two different isomers were observed experimentally from the di- to the pentahydrates (4-hydroxy-2-butanone-(H2O)n=2–5), including the 18O isotopologues for the di- and trihydrates. Interestingly, to accommodate water molecules effectively, the heavy atom skeleton of 4-hydroxy-2-butanone reshapes in every observed isomer and does not correspond to the stable conformer of the free monomer. All solvates initiate from the alcohol group (proton donor) but retain the carbonyl group as secondary binding point. The water scaffolds closely resemble those found in the pure water clusters, balancing between the capability of 4-hydroxy-2-butanone for steering the orientation and position of the water molecules and the ability of water to modulate the monomer's conformation. The present work thus provides an accurate molecular description on how torsionally flexible molecules dynamically adapt to water along progressing solvation

The first stages of nanomicelle formation captured in the sevoflurane trimer

Producción CientíficaSelf-aggregation of sevoflurane, an inhalable, fluorinated anesthetic, provides a challenge for current state-of-the-art high-resolution techniques due to its large mass and the variety of possible hydrogen bonds between monomers. Here we present the observation of sevoflurane trimer by chirped-pulse Fourier transform microwave spectroscopy, identified through the interplay of experimental and computational methods. The trimer (>600 Da), one of the largest molecular aggregates observed through rotational spectroscopy, does not resemble the binding (C–H···O) motif of the already characterized sevoflurane dimer, instead adapting a new binding configuration created predominantly from 17 CH···F hydrogen bonds that resembles a nanomicellar arrangement. The observation of such a heavy aggregate highlights the potential of rotational spectroscopy to study larger biochemical systems in the limit of spectroscopic congestion but also showcases the challenges ahead as the mass of the system increases.NSF Major Research Instrumentation program (grant CHE0960074)Ministerio de Ciencia, Innovación y Universidades - Fondo Europeo de Desarrollo Regional (grant PGC2018-098561-B-C22

Hydrogen Bonding in the Dimer and Monohydrate of 2-Adamantanol: A Test Case for Dispersion-Corrected Density Functional Methods

Weakly-bound intermolecular clusters constitute reductionist physical models for non-covalent interactions. Here we report the observation of the monomer, the dimer and the monohydrate of 2-adamantanol, a secondary alcohol with a bulky ten-carbon aliphatic skeleton. The molecular species were generated in a supersonic jet expansion and characterized using broadband chirped-pulse microwave spectroscopy in the 2–8 GHz frequency region. Two different gauche-gauche O-H···O hydrogen-bonded isomers were observed for the dimer of 2-adamantanol, while a single isomer was observed for the monomer and the monohydrate. The experimental rotational parameters were compared with molecular orbital calculations using density functional theory (B3LYP-D3(BJ), B2PLYP-D3(BJ), CAM-B3LYP-D3(BJ), ωB97XD), additionally providing energetic and electron density characterization. The shallow potential energy surface makes the dimer an interesting case study to benchmark dispersion-corrected computational methods and conformational search procedures