<i>Ab initio</i> study of hydrogen bonding in the phenol–water system

Feller, David; Feyereisen, Martin W.

doi:10.1002/jcc.540140904

Cited by 103 publications

(92 citation statements)

References 27 publications

(2 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…−7 to −8 kcal/mol at the MP2/aug-cc-pVDZ level. 20 Thus, the substituent effects were explored with the HF/6-311+G(d, p) and MP2/6-311+G(d, p) calculations. Counterpoise corrections have not been made since they are expected to show little variation with the choice of substituent X.…”

Section: Computational Detailsmentioning

confidence: 99%

Polarization Effects for Hydrogen-Bonded Complexes of Substituted Phenols with Water and Chloride Ion

Jorgensen

Jensen

Alexandrova

2007

J. Chem. Theory Comput.

101

View full text Add to dashboard Cite

Variations in hydrogen-bond strengths are investigated for complexes of nine para-substituted phenols (XPhOH) with a water molecule and chloride ion. Results from ab initio HF/6-311+G(d, p) and MP2/6-311+G(d, p)//HF/6-311+G(d, p) calculations are compared with those from the OPLS-AA and OPLS/CM1A force fields. In the OPLS-AA model, the partial charges on the hydroxyl group of phenol are not affected by the choice of para substituent, while the use of CM1A charges in the OPLS/CM1A approach does provide charge redistribution. The ab initio calculations reveal a 2.0-kcal/mol range in hydrogen-bond strengths for the XPhOH⋯OH 2 complexes in the order X = NO 2 > CN > CF 3 > Cl > F > H >OH >CH 3 > NH 2 . The pattern is not well-reproduced with OPLS-AA, which also compresses the variation to 0.7 kcal/mol. However, the OPLS/CM1A results are in good accord with the ab initio findings for both the ordering and range, 2.3 kcal/mol. The hydrogen bonding is, of course, weaker with XPhOH as acceptor, the order for X is largely inverted, and the range is reduced to ca. 1.0 kcal/mol. The substituent effects are found to be much greater for the chloride ion complexes with a range of 11 kcal/mol. For quantitative treatment of such strong ion-molecule interactions the need for fully polarizable force fields is demonstrated.

show abstract

Section: Computational Detailsmentioning

confidence: 99%

Polarization Effects for Hydrogen-Bonded Complexes of Substituted Phenols with Water and Chloride Ion

Jorgensen

Jensen

Alexandrova

2007

J. Chem. Theory Comput.

101

View full text Add to dashboard Cite

show abstract

“…Nevertheless, in recent years, several MP2 calculations have been reported in which the authors neglected to carefully investigate the forms of the normal modes. 33,34 This may cause an erroneous assignment of the MP2-calculated frequencies of phenol and its hydrogen-bonded complexes.…”

Section: (C6-h)(+53) ν(C4-h)(+21) ν(C5-h)(+20)mentioning

confidence: 99%

“Troublesome” Vibrations of Aromatic Molecules in Second-Order Möller−Plesset and Density Functional Theory Calculations: Infrared Spectra of Phenol and Phenol-OD Revisited

et al. 2001

View full text Add to dashboard Cite

The infrared spectra of phenol and phenol-OD are thoroughly reinvestigated, to resolve the contradictory assignment of some vibrations. The harmonic frequencies, integrated IR intensities, and potential energy distribution (PED) have been calculated by the B3LYP method with the 6-311++G(df,pd) basis set. The Fourier transform infrared (FT-IR) spectra of phenol and phenol-OD have been measured in carbon tetrachloride and cyclohexane solutions, in the frequency range 3700-400 cm -1 , and the experimental integrated infrared intensities are reported. On the basis of the results obtained, the detailed assignment of all the fundamental modes of Ph-OH and Ph-OD are presented. The study demonstrates that density functional B3LYP is clearly superior to the ab initio Hartree-Fock (HF) and second-order Möller-Plesset (MP2) methods in reliable prediction of the vibrational spectra of phenol. In particular, it is shown that scaling of the B3LYP-calculated frequencies of the CH and OH(OD) stretching vibrations by the scaling factor, derived by Baker et al. [J. Phys. Chem. A 1998, 102, 1412 gives excellent agreement between theoretical and experimental frequencies of these vibrations. Detailed theoretical investigations are performed for these troublesome normal modes in phenol and benzene, which show the largest deviations between the MP2-predicted frequencies and the experimental ones. It has been demonstrated that these modes have almost identical atomic displacements and potential energy distributions in both the molecules. The electron correlation effects and basis set dependences are examined, and the nature of these problematical vibrations in aromatic molecules is discussed.

show abstract

“…Therefore, systematic study on the hydrogen bond can reveal invaluable information for the structure and biochemical activity of protein. Since there are extremely many solvent molecules in the solution phase, however, it is more useful to study the hydrogen bonding in the clusters [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] consisting of a solute and a few solvent molecules.…”

Section: Introductionmentioning

confidence: 99%

“…The phenol-(H 2 O) n clusters have been studied most intensively by many investigators [15][16][17][18][19][20][21][22] as the prototypical system for organic alcohol-water cluster. As depicted in Figure 1, the role of the OH group in the phenol-(H 2 O) n cluster can be either proton-donating or -accepting.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Bonding in Aromatic Alcohol-Water Clusters: A Brief Review

2003

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

Recent experimental and theoretical advances on the aromatic alcohol-water clusters are reviewed, focusing on the structure of the hydrogen bonding between the alcoholic OH group and the binding water molecules. The interplay of experimental observations and theoretical calculations for the elucidation of the structure is demonstrated for phenol-water, benzyl alcohol-water, substituted phenol-water, naphthol-water and tropolone -water clusters. Discussion is made on assigning the role (either proton-donating or -accepting) of the hydroxyl group by measuring the shifts of infrared frequency of the OH stretching mode in the cluster from that of bare aromatic alcohol for the experimental determination of the cluster structure.

show abstract

Ab initio study of hydrogen bonding in the phenol–water system

Cited by 103 publications

References 27 publications

Polarization Effects for Hydrogen-Bonded Complexes of Substituted Phenols with Water and Chloride Ion

Polarization Effects for Hydrogen-Bonded Complexes of Substituted Phenols with Water and Chloride Ion

“Troublesome” Vibrations of Aromatic Molecules in Second-Order Möller−Plesset and Density Functional Theory Calculations: Infrared Spectra of Phenol and Phenol-OD Revisited

Hydrogen Bonding in Aromatic Alcohol-Water Clusters: A Brief Review

Contact Info

Product

Resources

About