Which isomeric form of formaldehyde dimer is the most stable – a high-level coupled-cluster study

Dolgonos, Grygoriy

doi:10.1016/j.cplett.2013.08.073

Cited by 31 publications

(38 citation statements)

References 39 publications

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“…The two minima on the (H 2 CO) 2 PES have been described in the literature with interaction energies of −4.43 and −3.58 kcal/mol at the ae-CCSD(T)/CBS computational level (see Scheme 1). 70 One structure is stabilized by a pair of CH· · ·O H-bonds, while the other replaces one of the CH· · ·O bonds by an apparent attraction between C and O. (H 2 CS) 2 seems to be an unstable structure which leads to the dimerization of the monomers through the formation of a formal S-C covalent bond as has been described recently by Krantz et al 71 in the literature (see Scheme 1).…”

Section: Mp2mentioning

confidence: 75%

Complexation of n SO2 molecules (n = 1, 2, 3) with formaldehyde and thioformaldehyde

Azofra

Scheiner

2014

The Journal of Chemical Physics

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Ab initio and density functional theory calculations are used to examine complexes formed between H2CO and H2CS with 1, 2, and 3 molecules of SO2. The nature of the interactions is probed by a variety of means, including electrostatic potentials, natural bond orbital, atoms in molecules, energy decomposition, and electron density redistribution maps. The dimers are relatively strongly bound, with interaction energies exceeding 5 kcal/mol. The structures are cyclic, containing both a O/S⋯S chalcogen bond and a CH⋯O H-bond. Addition of a second SO2 molecule leads to a variety of heterotrimer structures, most of which resemble the original dimer, where the second SO2 molecule engages in a chalcogen bond with the first SO2, and a C⋯O attraction with the H2CX. Some cooperativity is apparent in the trimers and tetramers, with an attractive three-body interaction energy and shortened intermolecular distances.

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Section: Mp2mentioning

confidence: 75%

Complexation of n SO2 molecules (n = 1, 2, 3) with formaldehyde and thioformaldehyde

Azofra

Scheiner

2014

The Journal of Chemical Physics

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“…The obtained energy for this structure is − 4.55 kcal/mol [26]. Dolgonos [17] studied the structures I(Cs), II(C2h) at the same The calculated energy profile along the proposed routes for the production of P6, P7, and P8 at the B3LYP/6 311++G (3df, 3pd) level mol for structure I(C s ) and 0.71 kcal/ml for structure I(C s ) and 0.54 kcal/ml for structure II(C 2h ) are lower than our work. Ohno et al computed the relative energies of the dimer structures of I(C s ), II(C 2h ) at several methods such as the MP2, MP2(full), M06-2X, and B3LYP-D3.…”

Section: Comparison Of the Obtained Dimer And Trimer Complexes With Lmentioning

confidence: 87%

“…The electronic structures and spectra of formaldehyde dimers were studied by several researchers experimentally and theoretically [1,2,17,[26][27][28] Dornshuld et al investigated the minima structures of formaldehyde and thioformaldehyde dimers such as Karpfen studied the minima structures of some dimers such as trans-glyoxal, trans-acrolein, and formaldehyde. He optimized all stationary points at the MP2/aug-cc-pVTZ level and the precise energies computed at the CCSD(T)/ aug-cc-pVTZ level.…”

Section: Comparison Of the Obtained Dimer And Trimer Complexes With Lmentioning

confidence: 99%

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A computational study on multiple formaldehyde complexes and their possible chemical reactions as well as the catalytic effect in the gas phase

2020

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A theoretical investigation on the dimerization and trimerization of formaldehyde molecules has focused on the singlet potential energy surface. Based on the possible reaction pathways, twelve transition states, three intermediates, and eight final products are obtained. All of the stationary points structures are calculated at the DFT/B3LYP method with the 6-311++G (3df, 3pd) basis set. In the present study, the CCSD/6-311++G (3df, 3pd) level of calculations was used to determine the precise energies of all species in the single point format on the B3LYP method optimized structures. The thermodynamic parameters were obtained using the DFT method. Our results show that among the obtained adducts six adducts have negative values in the Gibbs free energy. Also, the catalytic effect of formaldehyde was explored in the formation of 2-hydroxyacetaldehyde.

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“…Subsequently, a nitrogen matrix isolation study by Nelander 3 and a pulsed-nozzle Fourier transform microwave study by Lovas et al 4 both suggested that the two subunits are equivalent in the dimer consistent with a C s potential energy minimum without a center of symmetry. From a theoretical point of view, the first ab initio study of (CH 2 O) 2 was reported by Del Bene et al 5 Subsequently, more sophisticated quantum chemical methodologies have been reported by Ford et al 6 and recently by both Dolgonos 7 and Tschumper et al 8 who predicted the existence of two different intermolecular potential energy minima with almost identical energies ( Fig. 1).…”

Section: Introductionmentioning

confidence: 98%

Probing the global potential energy minimum of (CH2O)2: THz absorption spectrum of (CH2O)2 in solid neon and para-hydrogen

Andersen

Voute

Mihrin

et al. 2017

The Journal of Chemical Physics

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The true global potential energy minimum configuration of the formaldehyde dimer (CHO), including the presence of a single or a double weak intermolecular CH⋯O hydrogen bond motif, has been a long-standing subject among both experimentalists and theoreticians as two different energy minima conformations of C and C symmetry have almost identical energies. The present work demonstrates how the class of large-amplitude hydrogen bond vibrational motion probed in the THz region provides excellent direct spectroscopic observables for these weak intermolecular CH⋯O hydrogen bond motifs. The combination of concentration dependency measurements, observed isotopic spectral shifts associated with H/D substitutions and dedicated annealing procedures, enables the unambiguous assignment of three large-amplitude infrared active hydrogen bond vibrational modes for the non-planar C configuration of (CHO) embedded in cryogenic neon and enriched para-hydrogen matrices. A (semi)-empirical value for the change of vibrational zero-point energy of 5.5 ± 0.3 kJ mol is proposed for the dimerization process. These THz spectroscopic observations are complemented by CCSD(T)-F12/aug-cc-pV5Z (electronic energies) and MP2/aug-cc-pVQZ (force fields) electronic structure calculations yielding a (semi)-empirical value of 13.7 ± 0.3 kJ mol for the dissociation energy D of this global potential energy minimum.

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Which isomeric form of formaldehyde dimer is the most stable – a high-level coupled-cluster study

Cited by 31 publications

References 39 publications

Complexation of n SO2 molecules (n = 1, 2, 3) with formaldehyde and thioformaldehyde

Complexation of n SO2 molecules (n = 1, 2, 3) with formaldehyde and thioformaldehyde

A computational study on multiple formaldehyde complexes and their possible chemical reactions as well as the catalytic effect in the gas phase

Probing the global potential energy minimum of (CH2O)2: THz absorption spectrum of (CH2O)2 in solid neon and para-hydrogen

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