On the performance of resonance assisted hydrogen bond theory in malonaldehyde derivatives

Nakhaei, Ebrahim; Nowroozi, Alireza

doi:10.1016/j.comptc.2016.09.029

Cited by 16 publications

(8 citation statements)

References 33 publications

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“…Whereas malonaldehyde is a much simpler case than acetylacetone the influence of different substituents to the H atoms in its photodynamics as well as in its hydrogen bond strength have been investigated only in a few studies. 29,[43][44][45][46][47] . In particular, little information is available on 2-chloromalonaldehyde (noted hereafter 2-ClMA).…”

Section: 42mentioning

confidence: 99%

“…They concern mainly theoretical calculations on the CCC form with a focus on the IHB. 29,43,44,47,48 The geometry, the barrier height for H transfer and the associated splitting in the ground state were calculated for different derivatives of MA obtained by the substitution of one of the H atoms in different positions. Rios et al 44 obtained an estimation of the ground state splitting of 22 cm -1 for MA, in good agreement with experimental data, 8,10 and of about 12 cm -1 for 2-ClMA.…”

Section: 42mentioning

confidence: 99%

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2-Chloromalonaldehyde, a model system of resonance-assisted hydrogen bonding: vibrational investigation

Gutiérrez-Quintanilla

Chevalier

Platakyté

et al. 2018

Phys. Chem. Chem. Phys.

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The chelated enol isomer of 2-chloromalonaldehyde (2-ClMA) is experimentally characterized for the first time by IR and Raman spectroscopies. The spectra are obtained by trapping the molecule in cryogenic matrices and analyzed with the assistance of theoretical calculations. Experiments were performed in argon, neon and para-hydrogen matrices. The results highlight puzzling matrix effects, beyond site effects, which are interpreted as due to a tunneling splitting of the vibrational levels related to the proton transfer along the internal hydrogen bond (IHB). 2-ClMA is thus one of the very few molecules in which the H tunneling has been observed in cryogenic matrices. The comparison with its parent molecule (malonaldehyde) shows experimentally and theoretically the weakening of the IHB upon chlorination, with a reduced cooperative effect in the resonance assisted hydrogen bond. In addition, the Cl substitution induces an important stabilization of two open enol conformers. These two open forms appear in the spectra of as-deposited samples, meaning that, in contrast with other well-studied molecules of the same family (β-dialdehydes and β-diketones), they are present in the gas phase at room temperature.

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Section: 42mentioning

confidence: 99%

Section: 42mentioning

confidence: 99%

2-Chloromalonaldehyde, a model system of resonance-assisted hydrogen bonding: vibrational investigation

Gutiérrez-Quintanilla

Chevalier

Platakyté

et al. 2018

Phys. Chem. Chem. Phys.

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“…There were also many in which this idea was followed. See, for some recent examples, [ 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 ], and references therein.…”

Section: Introductionmentioning

confidence: 99%

Resonance-Assisted Hydrogen Bond—Revisiting the Original Concept in the Context of Its Criticism in the Literature

Domagała

Simon

2021

IJMS

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In the presented research, we address the original concept of resonance-assisted hydrogen bonding (RAHB) by means of the many-body interaction approach and electron density delocalization analysis. The investigated molecular patterns of RAHBs are open chains consisting of two to six molecules in which the intermolecular hydrogen bond stabilizes the complex. Non-RAHB counterparts are considered to be reference systems. The results show the influence of the neighbour monomers on the unsaturated chains in terms of the many-body interaction energy contribution. Exploring the relation between the energy parameters and the growing number of molecules in the chain, we give an explicit extrapolation of the interaction energy and its components in the infinite chain. Electron delocalization within chain motifs has been analysed from three different points of view: three-body delocalization between C=C-C, two-body hydrogen bond delocalization indices and also between fragments (monomers). A many-body contribution to the interaction energy as well as electron density helps to establish the assistance of resonance in the strength of hydrogen bonds upon the formation of the present molecular chains. The direct relation between interaction energy and delocalization supports the original concept, and refutes some of the criticisms of the RAHB idea.

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“…1) which has been extensively studied theoretically for MA 1,2,3,4 and slightly less for 2-ClMA. 5,6,7 Infrared spectroscopy can bring key information on dynamics of this important and fundamental process in nature. 8 The H transfer between the two oxygens of MA has already been observed in the gas phase by means of a tunneling splitting of vibrational levels, 9,10,11 but seems to be blocked when MA is embedded in rare gas matrices.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular hydrogen tunneling in 2-chloromalonaldehyde trapped in solid para-hydrogen

Gutiérrez-Quintanilla

Chevalier

Platakyté

et al. 2020

Phys. Chem. Chem. Phys.

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On the performance of resonance assisted hydrogen bond theory in malonaldehyde derivatives

Cited by 16 publications

References 33 publications

2-Chloromalonaldehyde, a model system of resonance-assisted hydrogen bonding: vibrational investigation

2-Chloromalonaldehyde, a model system of resonance-assisted hydrogen bonding: vibrational investigation

Resonance-Assisted Hydrogen Bond—Revisiting the Original Concept in the Context of Its Criticism in the Literature

Intramolecular hydrogen tunneling in 2-chloromalonaldehyde trapped in solid para-hydrogen

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