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CONTEXT: The study of molecular aggregation effects on the electronic spectrum is essential for the development of optoelectronic devices. However, investigating the entire valence absorption spectrum of aggregates using quantum mechanical methods is a challenging task. In this work, we perform systematic simulations of the absorption spectrum of benzene molecular clusters up to 35 eV applying two approaches based on time-dependent density functional theory. The results show that depending on the dimer packing, different energy shifts occur for the symmetry allowed [Formula: see text] transition, in comparison to the monomer. The transition intensity increases for the band around 6 eV for larger aggregates from the monomer to dimers and tetramer, indicating the occurrence of the symmetry forbidden (in [Formula: see text] point group) [Formula: see text] [Formula: see text] transition. The benzene crystal exhibits a large redshift following the experimental spectrum. Also, the continuum regions of all spectra show a good agreement with the experiments both in gas and solid phases. METHODS: Geometry optimization of the monomer was carried out with Gaussian 09 software using the PBE0/def2-TZVP level of theory. We used dimers and tetramer molecular geometries extracted from the experimental crystal structure. The absorption spectra were directly obtained by the Liouville-Lanczos TDDFT approach with plane waves basis set or indirectly by TDDFT pseudo-spectra calculated in a [Formula: see text] basis followed by analytic continuation procedure to obtain complex polarizability. The former is available at Quantum ESPRESSO, and the latter was calculated using Gaussian 09 with the post-processing performed with a code previously developed in our group.

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The discovery of C60, C60+, and C70 in the interstellar medium has ignited a profound interest in the astrochemistry of fullerene and related systems. In particular, the presence of diffuse interstellar bands and their association with C60+ has led to the hypothesis that hydrogenated derivatives, known as fulleranes, may also exist in the interstellar medium and contribute to these bands. In this study, we systematically investigated the structural and spectroscopic properties of C60Hn+q (n = 0-4, q = 0,1) using an automated global minimum search and density functional theory calculations. Our results revealed novel global minimum structures for C60H2 and C60H4, distinct from previous reports. Notably, all hydrogenated fullerenes exhibited lower ionization potentials and higher proton affinities compared to C60. From an astrochemical perspective, our results exposed the challenges in establishing definitive spectroscopic criteria for detecting fulleranes using mid-infrared and UV-Vis spectroscopies. However, we successfully identified distinct electronic transitions in the near-infrared range that serve as distinctive signatures of cationic fulleranes. We strongly advocate for further high-resolution experimental studies to fully explore the potential of these transitions for the interstellar detection of fulleranes.

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In the present work, we revisit the spectrum of the hexacyanocobaltate(III) ion, [Co(CN)6]3-, which has been considered a prototype complex in the coordination chemistry, with modern quantum chemistry methods. The main features have been describing by revealing the role of different effects, such as vibronic coupling, solvation and spin-orbit coupling. The UV-vis spectrum is composed by two bands (1A1g → 1T1g and 1A1g → 1T2g), characterized by singlet-singlet metal-centered transitions, and a more intense third one, characterized by charge transfer transition. There is also a small band shoulder. The first two are symmetry-forbidden transitions in the Oh group. Their intensity can only be explained by a vibronic coupling mechanism. For the band shoulder, additional to vibronic coupling, spin-orbit coupling is also necessary, since the transition is characterized as singlet to triplet, 1A1g → 3T1g.

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A comparison of four approaches to account the vibronic coupling in photoabsorption is performed. The methods considered are nuclear ensemble (NE), direct vibronic coupling (DVC), adiabatic Hessian (AH), and vertical gradient (VG). The case study is the symmetry-forbidden [Formula: see text] [Formula: see text]A[Formula: see text] [Formula: see text] [Formula: see text] [Formula: see text]A[Formula: see text] (n [Formula: see text] [Formula: see text]) transition in formaldehyde. Being forbidden in the equilibrium geometry, this transition is entirely induced by vibronic coupling and constitutes an appropriate case to study the performance of different methods. From DVC, it is found that mode 1 (C=O out-of-plane bending) is the most inducing, followed by mode 6 (in-plane C-H asymmetric stretching) and finally by mode 2 (in-plane C-H asymmetric bending). We were able to correlate 17 out of 20 structures obtained from NE with these modes, showing that these two methods, although different in principle, give comparable results. The simulated spectra were obtained for all methods and compared, and each one has its own advantage. In what concerns the transition studied, NE gives the best description of the spectrum, DVC is the only one that easily gives an absolute value for OOS, and AH and VG are the computationally less expensive methods. From the latter two, VG is the less demanding on computational grounds, since it does not require the excited state Hessian.

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Rotational spectroscopy plays a major role in the field of observational astrochemistry, enabling the detection of more than 200 species including a plethora of complex organic molecules in different space environments. Those line detections allow correctly determining the sources and physical properties, as well as exploring their morphology, evolutionary stage, and chemical evolution pathways. In this context, quantum chemistry is a powerful tool to the investigation of the molecular inventory of astrophysical environments, guiding laboratory experiments and assisting in both line assignments and extrapolation of the experimental data to unexplored frequency ranges. In the present work, we start by briefly reviewing the rotational model Hamiltonian for asymmetric tops beyond the rigid-rotor approximation, including rotational-vibrational, centrifugal, and anharmonic effects. Then, aiming at further contributing to the recording and analysis of laboratory microwave spectroscopy by means of accessible, less demanding quantum chemical methods, we performed density functional theory (DFT) calculations of the spectroscopic parameters of astrochemically relevant species, followed by their rotational spectrum simulations. Furthermore, dispersion-correction effects combined with different functionals were also investigated. Case studies are the asymmetric tops H2CO, H2CS, c-HCOOH, t-HCOOH, and HNCO. Spectroscopic parameter predictions were overall very close to experiment, with mean percentage errors smaller than 1% for zeroth order and [Formula: see text] for first-order constants. We discuss the implications and impacts of those constants on spectrum simulations, and compare line-frequency predictions at millimeter wavelengths. Moreover, theoretical spectroscopic parameters of c-HCOOH and HNCO are introduced for the first time in this work.

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Ionization and fragmentation pathways induced by ionizing agents are key to understanding the formation of complex molecules in astrophysical environments. Acetonitrile (CH3CN), the simplest organic nitrile, is an important molecule present in the interstellar medium. In this work, DFT and MP2 calculations were performed in order to obtain the low energy structures of the most relevant cations formed from electron-stimulated ion desorption of CH3CN ices. Selected reaction pathways and spectroscopic properties were also calculated. Our results indicate that the most stable acetonitrile cation structure is CH2CNH+ and that hydrogenation can occur successively without isomerization steps until its complete saturation. Moreover, the stability of distinct cluster families formed from the interaction of acetonitrile with small fragments, such as CHn+, C2Hn+, and CHnCNH+, is discussed in terms of their respective binding energies. Some of these molecular clusters are stabilized by hydrogen bonds, leading to species whose infrared features are characterized by a strong redshift of the N-H stretching mode. Finally, the rotational spectra of CH3CN and protonated acetonitrile, CH3CNH+, were simulated using distinct computational protocols based on DFT, MP2, and CCSD(T) considering centrifugal distortion, vibrational-rotational coupling, and vibrational anharmonicity corrections. By adopting an empirical scaling procedure for calculating spectroscopic parameters, we were able to estimate the rotational frequencies of CH3CNH+ with an expected average error below 1 MHz for J values up to 10.

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Platinum- and palladium-based catalysts are commonly used in hydrogenation reactions, but they present a great disadvantage of being quite expensive. In most cases, they can be substituted by cheaper alternative catalysts formed by transition metal carbides, such as molybdenum carbide (Mo2C). Among the reactions that can be catalyzed by Mo2C, hydrodeoxygenation (HDO) presents a great technological interest, especially in biofuel production. Nonetheless, the selectivity of carbides in HDO reactions of fatty acids is not well understood yet. In the present work, the reaction mechanism of the acrylic acid HDO over Mo2C, a fatty acid model molecule, was studied by density functional theory (DFT), with Perdew-Burke-Ernzerhof (PBE) functional and periodic boundary conditions. A global mechanism is proposed, divided in four steps, from acrylic acid to propane. In the first reaction step, decomposition by C-OH bond cleavage, with 24 kcal mol- 1 of activation energy, dominates over C=C and C=O hydrogenation. This result is in line with the absence of propanoic acid among the products and the formation of acrolein, as shown in an experimental work previously published. The proposed global mechanism is in fair agreement with the experimental findings. The main product is propane, which has the same number of carbon atoms of the reactant. This mechanism can be viewed as a model for HDO of any fatty acid catalyzed by Mo2C, since acrylic acid has the minimal structural features of fatty acids, i.e., a carboxyl group and a C=C double bond. Graphical Abstract HDO over Mo2C provides a product with same carbon atoms number of the reactant.

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We report on direct measurement of all major ion-fragments and cluster-ions formed during high-energy electron impact of 2 keV on gaseous and condensed-phase pyridine. The ion-fragments of the parent pyridine cation are discussed in groups according to the number of atoms from the aromatic ring. The ion yield distributions within these groups show significant shifts towards higher masses for condensed pyridine compared to gaseous pyridine due to hydrogen migration. A wide spectrum of desorbed hydrogenated fragment-ions and ionic clusters with masses up to 320 u are observed for pyridine. The ion yields for the protonated parent molecule (C5H5NH+), the dehydrogenated dimer (C10H9N2+) and the dehydrogenated trimer (C15H12N3+) depend on the mass of the desorbing ionic clusters. The strongest cluster signals are assigned to binding between the parent cation and subunits of the pyridine molecule. Quantum-chemical calculations reveal that the formation of a bond between the pyridine molecules and a carbenium ion is crucial for the stability of selected cluster ions.

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Potential energy curves and inner-shell ionization energies of carbon monoxide, oxygen and nitrogen molecules were calculated using several forms of the inner-shell multiconfigurational self-consistent field (IS-MCSCF) method-a recently proposed protocol to obtain specifically converged inner-shell states at this level. The particular forms of the IS-MCSCF method designated IS-GVB-PP, IS-FVBL and IS-CASSCF stand for perfect pairing generalized valence bond, full valence bond-like MCSCF and complete active space self consistent field, respectively. A comparison of these different versions of the IS-MCSCF method was carried out for the first time. The results indicate that inner-shell states are described accurately even for the simplest version of the method (IS-GVB-PP). Dynamic correlation was recovered by multireference configuration interaction or multireference perturbation theory. For molecules not having equivalent atoms, all methods led to comparable and accurate transition energies. For molecules with equivalent atoms, the most accurate results were obtained by multireference perturbation theory. Scalar relativistic effects were accounted for using the Douglas-Kroll-Hess Hamiltonian.

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Potential energy curves for inner-shell states of nitrogen and carbon dioxide molecules are calculated by inner-shell complete active space self-consistent field (CASSCF) method, which is a protocol, recently proposed, to obtain specifically converged inner-shell states at multiconfigurational level. This is possible since the collapse of the wave function to a low-lying state is avoided by a sequence of constrained optimization in the orbital mixing step. The problem of localization of K-shell states is revisited by calculating their energies at CASSCF level based on both localized and delocalized orbitals. The localized basis presents the best results at this level of calculation. Transition energies are also calculated by perturbation theory, by taking the above mentioned MCSCF function as zeroth order wave function. Values for transition energy are in fairly good agreement with experimental ones. Bond dissociation energies for N(2) are considerably high, which means that these states are strongly bound. Potential curves along ground state normal modes of CO(2) indicate the occurrence of Renner-Teller effect in inner-shell states.