Rotational spectroscopy meets theory

Puzzarini, Cristina

doi:10.1039/c3cp44301a

Cited by 65 publications

(81 citation statements)

References 122 publications

(136 reference statements)

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“…[21,[28][29][30][31] As ingle conformer has been predicted for exo-2,3-epoxynorbornane, as expected from the steric constraints present in the bridged bicyclem otif. This conformer was optimized with the Møller-Plesset perturbation (MP2) and density functional theory (B3LYP and M06-2X functionals).…”

Section: Theoretical Calculationssupporting

confidence: 53%

Structural Distortion of the Epoxy Groups in Norbornanes: A Rotational Study of exo‐2,3‐Epoxynorbornane

et al. 2015

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Exo-2,3-epoxynorbornane is studied in the gas phase by pulsed jet Fourier transform microwave spectroscopy in the 4-18 GHz region. Six isotopologues were observed and characterized in their natural abundance. The experimental substitution and effective structures were obtained. Comparison with the structure of norbornane shows significant differences in several bond lengths and valence angles upon introduction of the epoxy group. All the work is supported by quantum chemical calculations.

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Section: Theoretical Calculationssupporting

confidence: 53%

Structural Distortion of the Epoxy Groups in Norbornanes: A Rotational Study of exo‐2,3‐Epoxynorbornane

et al. 2015

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“…As demonstrated in Refs. , hyperfine parameters can be quantitatively computed by means of coupled‐cluster techniques, with relative uncertainties as small as 1–2% (which usually means absolute uncertainties smaller than 100 kHz for nuclear quadrupole‐coupling constants and smaller than 1 kHz for spin‐rotation constants). A significant example is provided by the recent detection of CF + in the Horsehead and Orion Bar photo‐dissociation regions (PDRs) .…”

Section: Perspectives and Conclusionmentioning

confidence: 99%

Astronomical complex organic molecules: Quantum chemistry meets rotational spectroscopy

Puzzarini

2016

Int J of Quantum Chemistry

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Astrochemistry is an interdisciplinary field involving chemistry, physics, and astronomy, which encompasses astronomical observations, modeling, as well as theoretical and experimental laboratory investigations. In the frame of the latter, this contribution provides an overview on the computational approaches supporting and complementing rotational spectroscopy experiments applied to astrochemical studies. The focus is on the computational strategies that permit accurate computations of structural and rotational parameters as well as of energetics and on their application to case studies, with particular emphasis on the so-called "astronomical complex" organic molecules.computational astrochemistry, complex organic molecules, computational composite schemes, rotational spectroscopy, quantum-chemical calculations | I N T R O D U C T I O NFor many years, the interstellar medium (ISM) was considered too hostile for organic species to be formed. This paradigm of thought began to deteriorate roughly forty years ago with the discovery of molecules containing carbon chains and rings. As time has gone on, the pace of molecular discovery has accelerated, and the detection in the last decade of molecules showing some significant complexity, like for example, glycolaldehyde (CH 2 OHCHO), [1] acetamide (CH 3 C(O)NH 2 ), [2] and methyl acetate (CH 3 OC(O)CH 3 ), [3] has changed this view dramatically. [4] Indeed, the detection of almost 200 molecules in interstellar or circumstellar shells [5] suggests that the ISM is characterized by a rich chemistry. [4] Among the "complex" organic molecules detected, where complexity has to be considered in relative terms, that is, from an astronomical point of view, the potentially prebiotic molecules have been attracted particular interest in relation to the issue of how life has been originated. [6] The debate on the origin of the biomolecule building blocks has been further stimulated by the discovery of nucleobases and amino acids in meteorites and in other space environments (see, for example, Refs. [7,8]).Understanding the chemical evolution of the universe is one of the main aim of astrochemistry, [4,6] which is an interdisciplinary field involving chemistry, physics, and astronomy, encompassing astronomical observations, modeling, as well as theoretical and experimental laboratory investigations. The starting point for the development of astrochemical models is the knowledge whether a molecule is present in the astronomical environment considered and, if so, its abundance. In this scenario, molecular spectroscopy plays a crucial role since the astronomical observation of spectroscopic signatures provides the unequivocal proof of the presence of chemical species. [9] It has also to be mentioned that, in addition to composition (by knowing which atom, ion or molecule produces the observed transition) and the corresponding abundance, several information about astronomical objects can be inferred from the analysis of the astronomical spectrum; in particular, physical parame...

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“…The theoretical description of systems that involve weak interaction is sensitive to basis set quality and to the level at which electron correlation is accounted for. Calculations by Puzzarini and Peterson [19] confirmed that electron correlation at the CCSD(T) level with large basis sets (the inclusion of high angular momentum functions [20] ) is required to achieve high accuracy. Therefore, the 19-valence electron (5s 2 5p 6 5d 10 6s 1 ) relativistic pseudopotential and its matching (37s33p22d2f1g)/ [5s5p4d2f1g] basis sets have been used for the Au atom.…”

Section: Computational Detailsmentioning

confidence: 99%

Metalophilic interaction in gold halide: Quantum chemical study of AuX (X = Fat)

2014

J Comput Chem

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Quantum chemical calculations of the structures, stabilities, and metalophilic interactions of AuX halides (X = F-At) at the CCSD(T) theoretical level with extended basis sets were performed. Natural bond orbital analysis showed that the present gold-halide metalophilic interactions mainly resulted from the overlap of an sp hybrid on halogen and a 6s6p5d hybrid on the Au atom. Analysis of electron density deformation showed a pronounced charge accumulation in the middle of the region between heavier X and Au, and clearly suggested the formation of covalent bond. Topological analysis of the Laplacian and total electronic energy densities at bond critical points showed the "intermediate type" character of gold-halide metalophilic interactions. Electron localization function showed the increased covalency from X = F to X = At.

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Rotational spectroscopy meets theory

Cited by 65 publications

References 122 publications

Structural Distortion of the Epoxy Groups in Norbornanes: A Rotational Study of exo‐2,3‐Epoxynorbornane

Structural Distortion of the Epoxy Groups in Norbornanes: A Rotational Study of exo‐2,3‐Epoxynorbornane

Astronomical complex organic molecules: Quantum chemistry meets rotational spectroscopy

Metalophilic interaction in gold halide: Quantum chemical study of AuX (X = Fat)

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