Computational Study of Noncovalent Complexes between Formamide and Formic Acid

Sánchez-García, Elsa; Montero, Luis A.; Sander, Wolfram

doi:10.1021/jp0553636

Cited by 22 publications

(24 citation statements)

References 41 publications

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“…The multiple minima hypersurface (MMH) approach [19,[36][37][38][39][40] was used for searching minima of the acetylene-furan dimers. One thousand randomly arranged structures were generated as starting points, and the resulting geometries were optimized and analyzed using the PM3 [41,42] and AM1 [43] semiempirical quantum mechanical Hamiltonians.…”

Section: Methodsmentioning

confidence: 99%

Ab initio and matrix isolation study of the acetylene–furan dimer

et al. 2008

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Section: Methodsmentioning

confidence: 99%

Ab initio and matrix isolation study of the acetylene–furan dimer

et al. 2008

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“…placed at the centre of a cube of defined side length, and extensively applied to study the microhydration and noncovalent interaction of molecular complexes. [38][39][40][41][42][43]…”

Section: Localisation Of Stationary Points On the Pes Of Carboxylic Amentioning

confidence: 99%

Density Functional Theory Study of the Oligomerization of Carboxylic Acids

Tommaso

Watson

2014

J. Phys. Chem. A

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We present a density functional theory [M06-2X/6-31+G(d,p)] study of the structures and free energies of formation of oligomers of four carboxylic acids (formic acid, acetic acid, tetrolic acid, and benzoic acid) in water, chloroform, and carbon tetrachloride. Solvation effects were treated using the SMD continuum solvation model. The low-lying energy structures of molecular complexes were located by adopting an efficient search procedure to probe the potential energy surfaces of the oligomers of carboxylic acids (CA)n (n = 2-6). The free energies of the isomers of (CA)n in solution were determined as the sum of the electronic energy, vibrational-rotational-translational gas-phase contribution, and solvation free energy. The assessment of the computational protocol adopted in this study with respect to the dimerization of acetic acid, (AA)2, and formic acid, (FA)2, located new isomers of (AA)2 and (FA)2 and gave dimerization constants in good agreement with the experimental values. The calculation of the self-association of acetic acid, tetrolic acid, and benzoic acid shows the following: (i) Classic carboxylic dimers are the most stable isomer of (CA)2 in both the gas phase and solution. (ii) Trimers of carboxylic acid are stable in apolar aprotic solvents. (iii) Molecular clusters consisting of two interacting classic carboxylic dimers (CA)4,(D+D) are the most stable type of tetramers, but their formation from the self-association of classic carboxylic dimers is highly unfavorable. (iv) For acetic acid and tetrolic acid the reactions (CA)2 + 2CA → (CA)4,(D+D) and (CA)3 + CA → (CA)4,(D+D) are exoergonic, but these aggregation pathways go through unstable clusters that could hinder the formation of tetrameric species. (v) For tetrolic acid the prenucleation species that are more likely to form in solution are dimeric and trimeric structures that have encoded structural motifs resembling the α and β solid forms of tetrolic acid. (vi) Stable tetramers of benzoic acid could form in carbon tetrachloride from the aggregation of trimers and monomers. (vii) Higher order clusters such as acetic acid pentamers and tetrolic acid hexamers are highly unstable in all solvation environments.

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“…[38][39][40] Their further role in protein structure, folding and stability can be well anticipated. 37,[41][42][43] There are numerous reports on hydrogen bonded carbonyl complexes by theoreticians and experimentalists [44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61] in the past and even today. [62][63][64][65][66][67][68] For example, the earlier work by Bobadova-Parvanova and his co-worker investigated the hydrogen bonded complexes between open-chain substituted aliphatic carbonyl compounds and hydrogen fluoride at the HF/6-31G * * level.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Characterization of Hydrogen Bonding Interactions between RCHO (R = H, CN, CF3, OCH3, NH2) and HOR′(R′ = H, Cl, CH3, NH2, C(O)H, C6H5)

Kaur

2015

J Chem Sci

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In this work, density functional theory and ab initio molecular orbital calculations were used to investigate the hydrogen bonded complexes of type RCHO· · · HOR (R = H, CN, CF 3 , OCH 3 , NH 2 ; R = H, Cl, CH 3 , NH 2 , C(O)H, C 6 H 5 ) employing 6-31++g** and cc-pVTZ basis sets. Thus, the present work considers how the substituents at both the hydrogen bond donor and acceptor affect the hydrogen bond strength. From the analysis, it is reflected that presence of -OCH 3 and -NH 2 substituents at RCHO greatly strengthen the stabilization energies, while -CN and -CF 3 decrease the same with respect to HCHO as hydrogen bond acceptor. The highest stabilization results in case of (H 2 N)CHO as hydrogen bond acceptor. The variation of the substituents at -OH functional group also influences the strength of hydrogen bond; nearly all the substituents increase the stabilization energy relative to HOH. The analysis of geometrical parameters; proton affinities, charge transfer, electron delocalization studies have been carried out.

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Computational Study of Noncovalent Complexes between Formamide and Formic Acid

Cited by 22 publications

References 41 publications

Ab initio and matrix isolation study of the acetylene–furan dimer

Ab initio and matrix isolation study of the acetylene–furan dimer

Density Functional Theory Study of the Oligomerization of Carboxylic Acids

Theoretical Characterization of Hydrogen Bonding Interactions between RCHO (R = H, CN, CF3, OCH3, NH2) and HOR′(R′ = H, Cl, CH3, NH2, C(O)H, C6H5)

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