Noncovalent Complexes between Dimethyl Ether and Formic Acid—An Ab Initio and Matrix Isolation Study

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

doi:10.1002/cphc.200400430

Cited by 21 publications

(25 citation statements)

References 35 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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“…Matrix-isolation infrared spectroscopy is a powerful method to study weakly bonded species, − and a fair number of the FA and N 2 O complexes have been prepared in cryogenic matrices. − The conformational change is another successful direction of research at low temperatures. The higher-energy conformer of formic acid, cis -FA, can be prepared in cryogenic matrices by selective vibrational excitation of the ground-state conformer, trans -FA (see Scheme for the structures of these conformers). − The cis -FA molecules isolated in cryogenic matrices are not stable, and they convert back to trans- FA by hydrogen-atom tunneling. − The cis -FA complexes can be made by using selective vibrational excitation of trans -FA often combined with annealing of the matrix.…”

Section: Introductionmentioning

confidence: 99%

Complex between Formic Acid and Nitrous Oxide: A Matrix-Isolation and Computational Study

2017

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The complex of formic acid (FA, HCOOH) with nitrous oxide (NO) was studied experimentally and computationally. Eight structures of the trans-FA···NO complex and nine structures of the cis-FA···NO complex were found at the density functional theory (M06-2X and wB97XD), MP2(full), and CCSD(T)-F12a levels. Two structures of the trans-FA···NO complex (1t and 3t) and two structures of the cis-FA···NO complex (1c and 3c) were identified by infrared spectroscopy in an argon matrix. Structure 1t with the bonded OH group appears in the matrices after deposition. Structures 3t and 3c with the free OH groups were prepared by vibrational excitation of the trans-FA conformer in structures 1t and 3t, respectively. Structure 3t is thermally unstable and relaxes to structure 1t at ∼15 K. Structure 1c with the bonded OH group is made by vibrational excitation of trans-FA monomer combined with thermal annealing. The lifetimes of the cis-FA···NO complex structures 1c (81.5 min) and 3c (18.7 min) in an argon matrix at 4.3 K are longer than that of cis-FA monomer (6.3 min). This difference agrees with the calculated stabilization barriers of these species.

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Noncovalent Complexes between Dimethyl Ether and Formic Acid—An Ab Initio and Matrix Isolation Study

Cited by 21 publications

References 35 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

Complex between Formic Acid and Nitrous Oxide: A Matrix-Isolation and Computational Study

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