Describing the Disulfide Bond: From the Density Functional Theory and Back through the "Lego Brick" Approach.

Selected molecular species containing the disulfide bond, RSSR, have been considered, these ranging from hydrogen disulfide, HS (R = H), to diphenyl disulfide with R = CH. The aim of this work is two-fold: (i) to investigate different computational approaches in order to derive accurate equilibrium structures at an affordable cost, (ii) to employ the results from the first goal in order to benchmark cheaper methodologies rooted in the density functional theory. Among the strategies used for the accurate geometrical determinations, the semiexperimental approach has been exploited in combination with a reduced-dimensionality VPT2 model, without however obtaining satisfactory results.

The Semiexperimental Approach at Work: Equilibrium Structure of Radical Species.

The so-called semiexperimental (SE) approach is a powerful technique for obtaining highly accurate equilibrium structures for isolated systems. This Featured Article describes its extension to open-shell species, thus providing the first systematic investigation on radical equilibrium geometries to be used for benchmarking purposes. The small yet significant database obtained demonstrates that there is no reduction in accuracy when moving from closed-shell species to radicals.

Carbamic acid and its dimer: A computational study.

A recent work by Marks et al. on the formation of carbamic acid in NH -CO interstellar ices pointed out its stability in the gas phase and the concomitant production of its dimer. Prompted by these results and the lack of information on these species, we have performed an accurate structural, energetic and spectroscopic investigation of carbamic acid and its dimer.

Tracing Prebiotic Molecules: Rotational Spectroscopy of Deuterated Glycolaldehyde and ()-1,2-Ethenediol.

Glycolaldehyde, an important prebiotic molecule, along with its monodeuterated species and its higher energy tautomer, ()-1,2-ethenediol, has been detected in the interstellar medium. Although the elemental D/H ratio in the universe is only ∼1.6 × 10, the deuterium relative abundance in interstellar molecules might be by far larger than this.

Isomerism of : Accurate structural, energetic, and spectroscopic characterization.

A recent work [Ye et al. Mon. Not.

Rotational spectra and semi-experimental structures of furonitrile and its water cluster.

Rotational spectroscopy represents an invaluable tool for several applications: from the identification of new molecules in interstellar objects to the characterization of van der Waals complexes, but also for the determination of very accurate molecular structures and for conformational analyses. In this work, we used high-resolution rotational spectroscopic techniques in combination with high-level quantum-chemical calculations to address all these aspects for two isomers of cyanofuran, namely 2-furonitrile and 3-furonitrile. In particular, we have recorded and analyzed the rotational spectra of both of them from 6 to 320 GHz; rotational transitions belonging to several singly-substituted isotopologues have been identified as well.

Insights into the Molecular Structure and Spectroscopic Properties of HONCO: An Accurate Study.

In an effort to provide the first accurate structural and spectroscopic characterization of the quasi-linear chain HONCO in its electronic ground state, state-of-the-art computational approaches mainly based on coupled-cluster (CC) theory have been employed. Equilibrium geometries have been calculated by means of a composite scheme based on CC calculations that incorporates up to the quadruple excitations and accounts for the extrapolation to the complete basis set limit and core correlation effects. This approach is proven to provide molecular structures with an accuracy better than 0.

Hunting for interstellar molecules: rotational spectra of reactive species.

Interstellar molecules are often highly reactive species, which are unstable under terrestrial conditions, such as radicals, ions and unsaturated carbon chains. Their detection in space is usually based on the astronomical observation of their rotational fingerprints. However, laboratory investigations have to face the issue of efficiently producing these molecules and preserving them during rotational spectroscopy measurements.

Hyperfine-resolved spectra of HDS together with a global ro-vibrational analysis.

Despite their chemical simplicity, the spectroscopic investigation of light hydrides, such as hydrogen sulfide, is challenging due to strong hyperfine interactions and/or anomalous centrifugal-distortion effects. Several hydrides have already been detected in the interstellar medium, and the list includes H2S and some of its isotopologues. Astronomical observation of isotopic species and, in particular, those bearing deuterium is important to gain insights into the evolutionary stage of astronomical objects and to shed light on interstellar chemistry.

Computational Protocol for the Identification of Candidates for Radioastronomical Detection and Its Application to the CHNO Family of Isomers.

The CHNO family of isomers is relevant in astrochemistry, even though its members are still elusive in the interstellar medium. To identify the best candidate for astronomical detection within this family, we developed a new computational protocol based on the minimum-energy principle. This approach aims to identify the most stable isomer of the family and consists of three steps.

A rotational investigation of the three isomeric forms of cyanoethynylbenzene (HCC-CH-CN): benchmarking experiments and calculations using the "Lego brick" approach.

We report the study of three structural isomers of phenylpropiolonitrile (3-phenyl-2-propynenitrile, CH-CN) containing an alkyne function and a cyano group, namely -, -, and -cyanoethynylbenzene (HCC-CH-CN). The pure rotational spectra of these species have been recorded at room temperature in the millimeter-wave domain using a chirped-pulse spectrometer (75-110 GHz) and a source-frequency modulation spectrometer (140-220 GHz). Assignments of transitions in the vibrational ground state and several vibrationally excited states were supported by quantum chemical calculations using the so-called "Lego brick" approach [A.

Bringing Machine-Learning Enhanced Quantum Chemistry and Microwave Spectroscopy to Conformational Landscape Exploration: the Paradigmatic Case of 4-Fluoro-Threonine.

A combined experimental and theoretical study has been carried out on 4-fluoro-threonine, the only naturally occurring fluorinated amino acid. Fluorination of the methyl group significantly increases the conformational complexity with respect to the parent amino acid threonine. The conformational landscape has been characterized in great detail, with special attention given to the inter-conversion pathways between different conformers.

Insights into the molecular structure and infrared spectrum of the prebiotic species aminoacetonitrile.

Aminoacetonitrile is an interstellar molecule with a prominent prebiotic role, already detected in the chemically-rich molecular cloud Sagittarius B2(N) and postulated to be present in the atmosphere of the largest Saturn's moon, Titan. To further support its observation in such remote environments and laboratory experiments aimed at improving our understanding of interstellar chemistry, we report a thorough spectroscopic and structural characterization of aminoacetonitrile. Equilibrium geometry, fundamental bands as well as spectroscopic and molecular parameters have been accurately computed by exploiting a composite scheme rooted in the coupled-cluster theory that accounts for the extrapolation to the complete basis set limit and core-correlation effects.

Toward Accurate yet Effective Computations of Rotational Spectroscopy Parameters for Biomolecule Building Blocks.

The interplay of high-resolution rotational spectroscopy and quantum-chemical computations plays an invaluable role in the investigation of biomolecule building blocks in the gas phase. However, quantum-chemical methods suffer from unfavorable scaling with the dimension of the system under consideration. While a complete characterization of flexible systems requires an elaborate multi-step strategy, in this work, we demonstrate that the accuracy obtained by quantum-chemical composite approaches in the prediction of rotational spectroscopy parameters can be approached by a model based on density functional theory.

Connections between the accuracy of rotational constants and equilibrium molecular structures.

Rotational spectroscopy is the technique of choice for investigating molecular structures in the gas phase. Indeed, rotational constants are strongly connected to the geometry of the molecular system under consideration. Therefore, they are powerful tools for assessing the accuracy that quantum chemical approaches can reach in structural determinations.

Parity-pair-mixing effects in nonlinear spectroscopy of HDO.

A non-linear spectroscopic study of the HDO molecule is performed in the wavelength range of 1.36-1.42 m using noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy (NICE-OHMS).

Gas-Phase Computational Spectroscopy: The Challenge of the Molecular Bricks of Life.

Gas-phase molecular spectroscopy is a natural playground for accurate quantum-chemical computations. However, the molecular bricks of life (e.g.

Intersystem crossing in the entrance channel of the reaction of O(P) with pyridine.

Two quantum effects can enable reactions to take place at energies below the barrier separating reactants from products: tunnelling and intersystem crossing between coupled potential energy surfaces. Here we show that intersystem crossing in the region between the pre-reactive complex and the reaction barrier can control the rate of bimolecular reactions for weakly coupled potential energy surfaces, even in the absence of heavy atoms. For O(P) plus pyridine, a reaction relevant to combustion, astrochemistry and biochemistry, crossed-beam experiments indicate that the dominant products are pyrrole and CO, obtained through a spin-forbidden ring-contraction mechanism.

Exploiting the "Lego brick" approach to predict accurate molecular structures of PAHs and PANHs.

Polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocycles (PANHs) are important and ubiquitous species in space. However, their accurate structural and spectroscopic characterization is often missing. To fill this gap, we exploit the so-called "Lego brick" approach [Melli , , 2021, , 9904] to evaluate accurate rotational constants of some astrochemically relevant PAHs and PANHs.

Rotational Spectra of Unsaturated Carbon Chains Produced by Pyrolysis: The Case of Propadienone, Cyanovinylacetylene, and Allenylacetylene.

Several interstellar molecules are highly reactive unsaturated carbon chains, which are unstable under terrestrial conditions. Laboratory studies in support of their detection in space thus face the issue of how to produce these species and how to correctly model their rotational energy levels. In this work, we introduce a general approach for producing and investigating unsaturated carbon chains by means of selected test cases.

Unbiased disentanglement of conformational baths with the help of microwave spectroscopy, quantum chemistry, and artificial intelligence: The puzzling case of homocysteine.

An integrated experimental-computational strategy for the accurate characterization of the conformational landscape of flexible biomolecule building blocks is proposed. This is based on the combination of rotational spectroscopy with quantum-chemical computations guided by artificial intelligence tools. The first step of the strategy is the conformer search and relative stability evaluation performed by means of an evolutionary algorithm.