Fluorobenzene⋯water and difluorobenzene⋯water systems: An ab initio investigation

Tarakeshwar Pilarisetty, Kwang S. Kim, B. Brutschy

Research output: Contribution to journalArticle

91 Citations (Scopus)

Abstract

Recently, Brutschy and co-workers have reported the spectra of (substituted benzene)⋯(H2O)n systems. To investigate the possibility of these systems exhibiting a π-H kind of bonding interaction as observed in benzene⋯(H2O)n systems, we have carried out extensive ab initio calculations on different conformations of the fluorobenzene⋯(H2O) and p-difluorobenzene⋯(H2O) systems using various basis sets. Our results indicate that unlike the π interaction observed in benzene⋯(H2O)n, the O-H of the water molecule is involved in the formation of a six-membered ring system with the F-C-C-H of the aromatic ring. This six-membered ring which results from the formation of two H-bonds (water hydrogen and fluorine, water oxygen and benzene hydrogen), is extensively stabilized by electrostatic interactions. The strength of this σ-bonding interaction of water to fluorobenzene in C6H5F⋯H2O is nearly equal to the corresponding π-bonding interaction of water to benzene in C6H6⋯H2O. However the σ interaction of water to difluorobenzene in p-C6H4F2⋯H2O is somewhat higher than the π interaction in C6H6⋯H2O and slightly higher than the corresponding interaction in C6H5F⋯H2O. The frequency shifts of the predicted OH stretching modes are in reasonable agreement with the experimental vibrational frequency shifts for both C6H5F⋯H2O and p-C6H4F2⋯H2O.

Original languageEnglish (US)
Pages (from-to)8501-8512
Number of pages12
JournalJournal of Chemical Physics
Volume110
Issue number17
DOIs
StatePublished - May 1 1999
Externally publishedYes

Fingerprint

Benzene
Water
Fluorobenzenes
benzene
interactions
water
Hydrogen
frequency shift
rings
Fluorine
Vibrational spectra
Coulomb interactions
Stretching
Conformations
hydrogen
Oxygen
fluorine
Molecules
electrostatics
oxygen

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Fluorobenzene⋯water and difluorobenzene⋯water systems : An ab initio investigation. / Pilarisetty, Tarakeshwar; Kim, Kwang S.; Brutschy, B.

In: Journal of Chemical Physics, Vol. 110, No. 17, 01.05.1999, p. 8501-8512.

Research output: Contribution to journalArticle

@article{413e0348176646cb93bd988821f4c4bd,
title = "Fluorobenzene⋯water and difluorobenzene⋯water systems: An ab initio investigation",
abstract = "Recently, Brutschy and co-workers have reported the spectra of (substituted benzene)⋯(H2O)n systems. To investigate the possibility of these systems exhibiting a π-H kind of bonding interaction as observed in benzene⋯(H2O)n systems, we have carried out extensive ab initio calculations on different conformations of the fluorobenzene⋯(H2O) and p-difluorobenzene⋯(H2O) systems using various basis sets. Our results indicate that unlike the π interaction observed in benzene⋯(H2O)n, the O-H of the water molecule is involved in the formation of a six-membered ring system with the F-C-C-H of the aromatic ring. This six-membered ring which results from the formation of two H-bonds (water hydrogen and fluorine, water oxygen and benzene hydrogen), is extensively stabilized by electrostatic interactions. The strength of this σ-bonding interaction of water to fluorobenzene in C6H5F⋯H2O is nearly equal to the corresponding π-bonding interaction of water to benzene in C6H6⋯H2O. However the σ interaction of water to difluorobenzene in p-C6H4F2⋯H2O is somewhat higher than the π interaction in C6H6⋯H2O and slightly higher than the corresponding interaction in C6H5F⋯H2O. The frequency shifts of the predicted OH stretching modes are in reasonable agreement with the experimental vibrational frequency shifts for both C6H5F⋯H2O and p-C6H4F2⋯H2O.",
author = "Tarakeshwar Pilarisetty and Kim, {Kwang S.} and B. Brutschy",
year = "1999",
month = "5",
day = "1",
doi = "10.1063/1.478758",
language = "English (US)",
volume = "110",
pages = "8501--8512",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "17",

}

TY - JOUR

T1 - Fluorobenzene⋯water and difluorobenzene⋯water systems

T2 - An ab initio investigation

AU - Pilarisetty, Tarakeshwar

AU - Kim, Kwang S.

AU - Brutschy, B.

PY - 1999/5/1

Y1 - 1999/5/1

N2 - Recently, Brutschy and co-workers have reported the spectra of (substituted benzene)⋯(H2O)n systems. To investigate the possibility of these systems exhibiting a π-H kind of bonding interaction as observed in benzene⋯(H2O)n systems, we have carried out extensive ab initio calculations on different conformations of the fluorobenzene⋯(H2O) and p-difluorobenzene⋯(H2O) systems using various basis sets. Our results indicate that unlike the π interaction observed in benzene⋯(H2O)n, the O-H of the water molecule is involved in the formation of a six-membered ring system with the F-C-C-H of the aromatic ring. This six-membered ring which results from the formation of two H-bonds (water hydrogen and fluorine, water oxygen and benzene hydrogen), is extensively stabilized by electrostatic interactions. The strength of this σ-bonding interaction of water to fluorobenzene in C6H5F⋯H2O is nearly equal to the corresponding π-bonding interaction of water to benzene in C6H6⋯H2O. However the σ interaction of water to difluorobenzene in p-C6H4F2⋯H2O is somewhat higher than the π interaction in C6H6⋯H2O and slightly higher than the corresponding interaction in C6H5F⋯H2O. The frequency shifts of the predicted OH stretching modes are in reasonable agreement with the experimental vibrational frequency shifts for both C6H5F⋯H2O and p-C6H4F2⋯H2O.

AB - Recently, Brutschy and co-workers have reported the spectra of (substituted benzene)⋯(H2O)n systems. To investigate the possibility of these systems exhibiting a π-H kind of bonding interaction as observed in benzene⋯(H2O)n systems, we have carried out extensive ab initio calculations on different conformations of the fluorobenzene⋯(H2O) and p-difluorobenzene⋯(H2O) systems using various basis sets. Our results indicate that unlike the π interaction observed in benzene⋯(H2O)n, the O-H of the water molecule is involved in the formation of a six-membered ring system with the F-C-C-H of the aromatic ring. This six-membered ring which results from the formation of two H-bonds (water hydrogen and fluorine, water oxygen and benzene hydrogen), is extensively stabilized by electrostatic interactions. The strength of this σ-bonding interaction of water to fluorobenzene in C6H5F⋯H2O is nearly equal to the corresponding π-bonding interaction of water to benzene in C6H6⋯H2O. However the σ interaction of water to difluorobenzene in p-C6H4F2⋯H2O is somewhat higher than the π interaction in C6H6⋯H2O and slightly higher than the corresponding interaction in C6H5F⋯H2O. The frequency shifts of the predicted OH stretching modes are in reasonable agreement with the experimental vibrational frequency shifts for both C6H5F⋯H2O and p-C6H4F2⋯H2O.

UR - http://www.scopus.com/inward/record.url?scp=0042392958&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0042392958&partnerID=8YFLogxK

U2 - 10.1063/1.478758

DO - 10.1063/1.478758

M3 - Article

AN - SCOPUS:0042392958

VL - 110

SP - 8501

EP - 8512

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 17

ER -