Microhydration of small protonated polyaromatic hydrocarbons: a first principles study.

Using first principles methodology, we investigate the microsolvation of protonated benzene (BzH+), protonated coronene (CorH+) and protonated dodecabenzocoronene (DbcH+). Gas phase complexes of these small protonated polyaromatic hydrocarbons (H+PAHs) with mono-, di-, and tri-hydrated water molecules are considered. Their most stable forms are presented, where we discuss their structural, energetic aromaticity and IR and UV spectral features. In particular, we focus on the analysis of the bonding and various non-bonded interactions between these protonated aromatics and water clusters. The strength of non-bonded interactions is quantified and correlated with their electron density profiles. Furthermore, insights into the interfacial interactions and stability of these complexes were obtained through non-covalent index and symmetry-adapted perturbation theory (SAPT0) analyses. We also discuss the effects of the extension of the π aromatic cloud on the water solvation of these protonated aromatics. In particular, we extended our predictions for the S0 → S1 and S0 → T1 wavelength transitions of micro hydrated H+PAHs to deduce those of these species solvated in aqueous solution. The present findings should be useful for understanding, at the microscopic level, the effects of water interacting with H+PAHs, which are relevant for organic chemistry, astrochemistry, atmospheric chemistry, combustion and materials science.

DFT mechanistic study of the chemical fixation of CO2 by aziridine derivatives.

Using density functional theory (DFT), we treat the reaction of coupling of CO2 with aziridine in gas phase, in the presence of water and of a green catalyst (NaBr). Computations show that, in gas phase, this ring-opening conversions to oxazolidinones initiates by coordinating a CO2 molecule to the nitrogen atom of the aziridine. Then, a nucleophilic interaction between one oxygen atom of the coordinated CO2 and the carbon atom of the aziridine occurs. For methyl substituted aziridine, two pathways are proposed leading either to 4-oxazolidinone or to 5-oxazolidinone. Besides, we show that the activation energy of this reaction reduces in aqueous solution, in the presence of a water molecule explicitly or NaBr catalyst. In addition, the corresponding reaction mechanisms and regioselectivity associated with this ring-opening conversions to oxazolidinones, in the presence of carbon dioxide are found to be influenced by solvent and catalyst. The present findings should allow better designing regioisomer oxazolidinones relevant for organic chemistry, medicinal and pharmacological applications.

Insights into the mechanism of [3+2] cycloaddition reactions between N-benzyl fluoro nitrone and maleimides, its selectivity and solvent effects.

We present a theoretical study of the [3+2] cycloaddition (32CA) reactions of N-benzyl fluoro nitrone with a series of maleimides producing isoxazolidines. We use the Molecular Electron Density Theory at the MPWB1K/6-311G(d) level. We focus on the reaction mechanism, selectivity, solvent, and temperature effects. In addition, we perform topological analyses at the minimal and transition states to identify the intermolecular interactions. Electron Localization Function approach classifies the N-benzyl fluoro nitrone as zwitterionic (zw-) three-atom components (TACs), associated with a high energy barrier. The low polar character of the reaction is evaluated using the Conceptual Density Functional Theory analysis of the reactants, confirmed by the low global electron density transfer computed at the transition states. Computations show that these 32CA reactions follow a one-step mechanism under kinetic control, with highly asynchronous bond formation and no new covalent bond is formed at the TS. Besides, the potential energy surfaces along the reaction pathways in gas phase and in solvent are mapped. The corresponding Gibbs free energy profiles reveal that the exo-cycloadducts are kinetically and thermodynamically more favored than endo-cycloadducts, in agreement with the exo-selectivity observed experimentally. In particular, we found that solvent and temperature did not affect this selectivity and mainly influence the activation energies and the exothermic character of these 32CA reactions.

Temperature-Dependent Line-Broadening Effects in CO2 Caused by Ar.

This computational study of line-broadening effects is based on an accurate, analytical representation of the intermonomer potential energy surface (PES) of the CO2 ⋅ Ar van der Waals (vdW) complex. The PES is employed to compute collisional broadening coefficients for rovibrational lines of CO2 perturbed by Ar. The semiclassical computations are performed using the modified Robert-Bonamy approach, including real and imaginary terms, and the exact trajectory model. The lines investigated are in the 10001←00011, 01101←00001, 00011←00001, and 00031←00001 vibrational bands and the computations are repeated at multiple temperatures. The computed results are in good agreement with the available experimental values, validating both the intermonomer PES developed and the methodology used. For lines in the 01101←00001 band of CO2 , temperature-dependent Ar-broadening coefficients are reported for the first time. The parameters presented should prove useful, among other applications, for the accurate experimental determination of CO2 and Ar abundances in planetary atmospheres.

Insights into the Molecular Structure and Spectroscopic Properties of HONCO: An Accurate Ab Initio 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 0.001 Å and 0.05° for bond lengths and angles, respectively. Incorporation of vibrational effects permits this level of theory to predict rotational constants with an estimated accuracy of 0.1% or better. Vibrational fundamental bands have been evaluated by means of a hybrid scheme based on harmonic frequencies computed using the CC singles, doubles, and a perturbative treatment of the triples method (CCSD(T)) in conjunction with a quadruple-ζ basis set, with all electrons being correlated, and anharmonic corrections from CCSD(T) calculations using a triple-ζ basis set, within the frozen-core approximation. Such a hybrid approach allowed us to obtain fundamental frequencies with a mean absolute error of about 1%. To complete the spectroscopic characterization, vertical electronic excitation energies have been calculated for the lowest singlet and triplet states using the internally contracted multireference configuration interaction (MRCI) method. Computations show that HONCO dissociates into OH + NCO upon the absorption of UV-vis light. In conclusion, we are confident that the highly accurate spectroscopic data provided herein can be useful for guiding future experimental investigations and supporting the characterization of this molecule in atmospheric and astrophysical media, as well as in combustion.

Towards the generation of potential energy surfaces of weakly bound medium-sized molecular systems: the case of benzonitrile-He complex.

Currently, the explicitly correlated coupled cluster method is used routinely to generate the multi-dimensional potential energy surfaces (mD-PESs) of van der Waals complexes of small molecular systems relevant for atmospheric, astrophysical and industrial applications. Although very accurate, this method is computationally prohibitive for medium and large molecules containing clusters. For instance, the recent detections of complex organic molecules (COMs) in the interstellar medium, such as benzonitrile, revealed the need to establish an accurate enough electronic structure approach to map the mD-PESs of these species interacting with the surrounding gases. As a benchmark, we have treated the case of the polar molecule benzonitrile interacting with helium, where we use post-Hartree-Fock and symmetry-adapted perturbation theory (SAPT) techniques. Accordingly, we show that MP2 and distinguishable-cluster approximation (DCSD) cannot be used for this purpose, whereas accurate enough PESs may be obtained using the corresponding explicitly correlated versions (MP2-F12 or DCSD-F12) with a reduction in computational costs. Alternatively, computations revealed that SAPT(DFT) is as performant as CCSD(T)-F12/aug-cc-pVTZ, making it the method of choice for mapping the mD-PESs of COMs containing clusters. Therefore, we have used this approach to generate the 3D-PES of the benzonitrile-He complex along the intermonomer Jacobi coordinates. As an application, we have incorporated the analytic form of this PES into quantum dynamical computations to determine the cross sections of the rotational (de-)excitation of benzonitrile colliding with helium at a collision energy of 10 cm-1.

Accurate Prediction of Adiabatic Ionization Energies for PAHs and Substituted Analogues.

The accurate calculation of adiabatic ionization energies (AIEs) for polycyclic aromatic hydrocarbons (PAHs) and their substituted analogues is essential for understanding their electronic properties, reactivity, stability, and environmental/health implications. This study demonstrates that the M06-2X density functional theory method excels in predicting the AIEs of polycyclic aromatic hydrocarbons and related molecules, rivaling the (R)CCSD(T)-F12 method in terms of accuracy. These findings suggest that M06-2X, coupled with an appropriate basis set, represents a reliable and efficient method for studying polycyclic aromatic hydrocarbons and related molecules, aligning well with the experimental techniques. The set of molecules examined in this work encompasses numerous polycyclic aromatic hydrocarbons from m/z 67 up to m/z 1,176, containing heteroatoms that may be found in biofuels or nucleic acid bases, making the results highly relevant for photoionization experiments and mass spectrometry. For coronene-derivative molecular species with the C6n2H6n chemical formula, we give an expression to predict their AIEs (AIE (n) = 4.359 + 4.8743n-0.72057, in eV) upon extending the π-aromatic cloud until reaching graphene. In the long term, the application of this method is anticipated to contribute to a deeper understanding of the relationships between PAHs and graphene, guiding research in materials science and electronic applications and serving as a valuable tool for validating theoretical calculation methods.

The first HyDRA challenge for computational vibrational spectroscopy.

Vibrational spectroscopy in supersonic jet expansions is a powerful tool to assess molecular aggregates in close to ideal conditions for the benchmarking of quantum chemical approaches. The low temperatures achieved as well as the absence of environment effects allow for a direct comparison between computed and experimental spectra. This provides potential benchmarking data which can be revisited to hone different computational techniques, and it allows for the critical analysis of procedures under the setting of a blind challenge. In the latter case, the final result is unknown to modellers, providing an unbiased testing opportunity for quantum chemical models. In this work, we present the spectroscopic and computational results for the first HyDRA blind challenge. The latter deals with the prediction of water donor stretching vibrations in monohydrates of organic molecules. This edition features a test set of 10 systems. Experimental water donor OH vibrational wavenumbers for the vacuum-isolated monohydrates of formaldehyde, tetrahydrofuran, pyridine, tetrahydrothiophene, trifluoroethanol, methyl lactate, dimethylimidazolidinone, cyclooctanone, trifluoroacetophenone and 1-phenylcyclohexane-cis-1,2-diol are provided. The results of the challenge show promising predictive properties in both purely quantum mechanical approaches as well as regression and other machine learning strategies.

Doubly ionized OCS bond rearrangement upon fragmentation - experiment and theory.

The dissociation of OCS2+ ions formed by photoionization of the neutral molecule at 40.81 eV is examined using threefold and fourfold electron-ion coincidence spectroscopy combined with high level quantum chemical calculations on isomeric structures and their potential energy surfaces. The dominant dissociation channel of [OCS]2+ is charge separation forming CO+ + S+ ion pairs, found here to be formed with low intensity at a lower-energy onset and with a correspondingly smaller kinetic energy release than in the more intense higher energy channel previously reported. We explain the formation of CO+ + S+ ion pairs at low as well as higher ionization energies by the existence of two predissociation channels, one involving a newly identified COS2+ metastable state. We conclude that the dominant CO+ + S+ channel with 5.2 eV kinetic energy release is reached upon OCS2+ → COS2+ isomerization, whereas the smaller kinetic energy release (of ∼4 eV) results from the direct fragmentation of OCS2+ (X3Σ-) ions. Dissociation of the COS2+ isomer also explains the existence of the minor C+ + SO+ ion pair channel. We suggest that isomerization prior to dissociation may be a widespread mechanism in dications and more generally in multiply charged ion dissociations.

Symmetry breaking in core-valence double ionisation of allene.

Conventional electron spectroscopy is an established one-electron-at-the-time method for revealing the electronic structure and dynamics of either valence or inner shell ionized systems. By combining an electron-electron coincidence technique with the use of soft X-radiation we have measured a double ionisation spectrum of the allene molecule in which one electron is removed from a C1s core orbital and one from a valence orbital, well beyond Siegbahns Electron-Spectroscopy-for-Chemical-Analysis method. This core-valence double ionisation spectrum shows the effect of symmetry breaking in an extraordinary way, when the core electron is ejected from one of the two outer carbon atoms. To explain the spectrum we present a new theoretical approach combining the benefits of a full self-consistent field approach with those of perturbation methods and multi-configurational techniques, thus establishing a powerful tool to reveal molecular orbital symmetry breaking on such an organic molecule, going beyond Löwdins standard definition of electron correlation.

Formation of Eigen or Zundel Features at Protonated Water Cluster-Aromatic Interfaces.

Interfacial interactions of protonated water clusters adsorbed at aromatic surfaces play an important role in biology, and in atmospheric, chemical and materials sciences. Here, we investigate the interaction of protonated water clusters ((H+ H2 O)n (where n=1-3)) with benzene (Bz), coronene (Cor) and dodecabenzocoronene (Dbc)). To study the structure, stability and spectral features of these complexes, computations are done using DFT-PBE0(+D3) and SAPT0 methods. These interactions are probed by AIM electron density topography and non-covalent interactions index (NCI) analyses. We suggest that the excess proton plays a crucial role in the stability of these model interfaces through strong inductive effects and the formation of Eigen or Zundel features. Also, computations reveal that the extension of the π-aromatic system and the increase of the number of water molecules in the H-bounded water network led to a strengthening of the interactions between the corresponding aromatic compound and protonated water molecules, except when a Zundel ion is formed. The present findings may serve to understand in-depth the role of proton localized at aqueous medium interacting with large aromatic surfaces such as graphene interacting with acidic liquid water. Besides, we give the IR and UV-Vis spectra of these complexes, which may help for their identification in laboratory.

Photoionization Dynamics and Proton Transfer within the Adenine-Thymine Nucleobase Pair.

Studying the stability of hydrogen-bonded nucleobase pairs, at the heart of the genetic code, is of utmost importance for an in-depth understanding of basic mechanisms of life and biomolecular evolution. We present here a VUV single photon ionization dynamic study of the nucleobase pair adenine-thymine (AT), revealing its ionization and dissociative ionization thresholds via double imaging electron/ion coincidence spectroscopy. The experimental data, consisting of cluster mass-resolved threshold photoelectron spectra and photon energy-dependent ion kinetic energy release distributions, allow the unambiguous distinction of the dissociation of AT into protonated adenine AH+ and a dehydrogenated thymine radical T(-H) from dissociative ionization processes of other nucleobase clusters. Comparison to high-level ab initio calculations indicates that our experimental observations can be explained by a single hydrogen-bonded conformer present in our molecular beam and allows the estimation of an upper limit of the barrier of the proton transfer in the ionized AT pair.

Theoretical study of the CO2-O2 van der Waals complex: potential energy surface and applications.

A four-dimensional-potential energy surface (4D-PES) of the atmospherically relevant carbon dioxide-oxygen molecule (CO2-O2) van der Waals complex is mapped using the ab initio explicitly correlated coupled cluster method with single, double, and perturbative triple excitations (UCCSD(T)-F12b), and extrapolation to the complete basis set (CBS) limit using the cc-pVTZ-F12/cc-pVQZ-F12 bases and the l-3 formula. An analytic representation of the 4D-PES was fitted using the method of interpolating moving least squares (IMLS). These calculations predict that the most stable configuration of CO2-O2 complex corresponds to a planar slipped-parallel structure with a binding energy of V ∼ -243 cm-1. Another isomer is found on the PES, corresponding to a non-planar cross-shaped structure, with V ∼ -218 cm-1. The transition structure connecting the two minima is found at V ∼ -211 cm-1. We also performed comparisons with some CO2-X van der Waals complexes. Moreover, we provide a SAPT analysis of this molecular system. Then, we discuss the complexation induced shifts of CO2 and O2. Afterwards, this new 4D-PES is employed to compute the second virial coefficient including temperature dependence. A comparison between quantities obtained in our calculations and those from experiments found close agreement attesting to the high quality of the PES and to the importance of considering a full description of the anisotropic potential for the derivation of thermophysical properties of CO2-O2 mixtures.

Electronic Structure and Spectroscopy of the AuO+ Cation.

The electronic structure and spectroscopy of the 29 lowest electronic states of the AuO+ cation were studied using ab initio multiconfigurational methods. These states correlate to the Au+(1S) + O(3P) and Au+(3D) + O(3P) dissociation limits. Their potentials were calculated along the Au-O internuclear distance. There are 23 of these electronic states with potential wells deep enough to allow for long lifetimes of the AuO+ cation in the corresponding states. These bound electronic states were characterized spectroscopically by solving the radial Schrödinger equation for the nuclear motion, to deduce full sets of spectroscopic parameters. The effects of the spin-orbit coupling on the lowest electronic states have been studied by determining the potentials and spectroscopic constants of the seven lowest spin-orbit Ω components. We also carried out precise calculations to determine the adiabatic ionization energy of the AuO molecule, where several corrections of the electronic energies obtained with the standard coupled cluster approach were taken into account. Our results will facilitate the correct assignment of the IR, vis, and UV spectra of the AuO+ cation and the photoelectron spectrum of the neutral AuO diatomic.

Cryogenic IR and UV spectroscopy of isomer-selected cytosine radical cation.

Oxidation of the nucleobases is of great concern for the stability of DNA strands and is considered as a source of mutagenesis and cancer. However, precise spectroscopy data, in particular in their electronic excited states are scarce if not missing. We here report an original way to produce isomer-selected radical cations of DNA bases, exemplified in the case of cytosine, through the photodissociation of cold cytosine-silver (C-Ag+) complex. IR-UV dip spectroscopy of C-Ag+ features fingerprint bands for the two keto-amino cytosine tautomers. UV photodissociation (UVPD) of the isomer-selected C-Ag+ complexes produces the cytosine radical cation (C˙+) without isomerization. IR-UV cryogenic ion spectroscopy of C˙+ allows for the unambiguous structural assignment of the two keto-amino isomers of C˙+. UVPD spectroscopy of the isomer-selected C˙+ species is recorded at a unique spectral resolution. These benchmark spectroscopic data of the electronic excited states of C˙+ are used to assess the quantum chemistry calculations performed at the TD-DFT, CASSCF/CASPT2 and CASSCF/MRCI-F12 levels.