Phenol O–H bond dissociation energy in water clusters

Couto, P. Cabral do; Guedes, Rita C.; Cabral, Benedito J. Costa; Simões, José A. Martinho

doi:10.1002/qua.1110

Cited by 28 publications

(6 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The numerous calculations of O−H BDE in phenol up to 1997 have been summarized by Borges dos Santos and Martinho Simoes . More recently, 13 different computational strategies yielded BDE(C 6 H 5 O−H)s ranging from 81.7 to 100.3 kcal mol -1 . Previous work by some of us using density functional theory (DFT) based methods gave values in the range 87.0 ± 0.3 or 87.9 ± 0.9 kcal mol -1 , depending on the level of theory at which the geometries were optimized and whether a (RO)B3LYP/6-311+G(2d,2p) or (U)B3P86/6-311G(2d,2p) approach was employed to calculate single point energies .…”

Section: Resultsmentioning

confidence: 99%

Critical Re-evaluation of the O−H Bond Dissociation Enthalpy in Phenol

et al. 2005

View full text Add to dashboard Cite

Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=61fe7128-8efa-4f51-847f-6a0f4fb214ed http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=61fe7128-8efa-4f51-847f-6a0f4fb214ed Science, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR6 ReceiVed: June 25, 2001; In Final Form: October 25, 2001 The results of density functional theory (DFT) energy calculations and geometry optimizations for selected planar and ruffled conformers of nickel octaethylporphyrin (NiOEP) are reported. Calculated geometric parameters show remarkably good agreement with experimental X-ray crystallography data. The tendency for ruffling of the porphyrin macrocycle to allow for a shorter Ni-N bond is accurately predicted by DFT calculations. Energy values indicate that ruffling of the macrocycle lowers the energy of the different conformers by about 0.2 kcal/mol.

show abstract

Section: Resultsmentioning

confidence: 99%

Critical Re-evaluation of the O−H Bond Dissociation Enthalpy in Phenol

et al. 2005

View full text Add to dashboard Cite

show abstract

“…Enthalpies were also computed using two composite procedures, namely, CBS-Q and CBS-QB3, – as well as with a dual (D,T) scheme to complete basis set extrapolation of CCSD(T) energies relying on cc-pVDZ and cc-pVTZ calculations proposed by Truhlar . This was necessary since previous works have shown that DFT behaves erratically in the determination of bond dissociation enthalpies. , The CBS methods, particularly CBS-QB3, as well as the (D,T) extrapolation, have shown to be adequate tools for the study of BDEs . The B3LYP/cc-pVTZ calculations were also used to determine Mulliken atomic spin densities – for the radical species under study.…”

Section: Methodsmentioning

confidence: 99%

Energetic Differences between the Five- and Six-Membered Ring Hydrocarbons: Strain Energies in the Parent and Radical Molecules

et al. 2008

View full text Add to dashboard Cite

The C-H bond dissociation enthalpies (BDEs) for the five- and six-membered ring alkanes, alkenes, and dienes were investigated and discussed in terms of conventional strain energies (SEs). New determinations are reported for cyclopentane and cyclohexane by time-resolved photoacoustic calorimetry and quantum chemistry methods. The C-H BDEs for the alkenes yielding the alkyl radicals cyclopenten-4-yl and cyclohexen-4-yl and the alpha-C-H BDE in cyclopentene were also calculated. The s-homodesmotic model was used to determine SEs for both the parent molecules and the radicals. When the appropriate s-homodesmotic model is chosen, the obtained SEs are in good agreement with the ones derived from group additivity schemes. The different BDEs in the title molecules are explained by the calculated SEs in the parent molecules and their radicals: (1) BDEs leading to alkyl radicals are ca. 10 kJ mol (-1) lower in cyclopentane and cyclopentene than in cyclohexane and cyclohexene, due to a smaller eclipsing strain in the five-membered radicals relative to the parent molecules (six-membered hydrocarbons and their radicals are essentially strain free). (2) C-H BDEs in cyclopentene and cyclohexene leading to the allyl radicals are similar because cyclopenten-3-yl has almost as much strain as its parent molecule, due to a synperiplanar configuration. (3) The C-H BDE in 1,3-cyclopentadiene is 27 kJ mol (-1) higher than in 1,4-cyclohexadiene due to the stabilizing effect of the conjugated double bond in 1,3-cyclopentadiene and not to a destabilization of the cyclopentadienyl radical. The chemical insight afforded by group additivity methods in choosing the correct model for SE estimation is highlighted.

show abstract

“…A number of studies have shown phenol–phenol or phenol-water clusters can form in the gas-phase and produce stable clusters through hydrogen bonding. − Theoretical simulations predict the stability of phenol-water clusters to be comparable to that of water clusters, exhibiting similar hydrogen bonding energies. , While no studies have investigated nitrophenol gas-phase clustering, these compounds are known to form both intra- and intermolecular hydrogen bonds; with very strong intramolecular hydrogen bonding observed between the nitro and hydroxyl group (C–NO–HO-C). − Such interactions could result in stabilized cluster formation and new particle formation, potentially accounting for the observations shown in Sato et al (2012) and in this study; although this remains to be explained.…”

Section: Resultsmentioning

confidence: 99%

“…A number of studies have shown phenol-phenol or phenol-water clusters can form in the gas-phase and produce stable clusters through hydrogen bonding [71][72][73][74] . Theoretical simulations predict the stability of phenol-water clusters to be comparable to that of water clusters, exhibiting similar hydrogen bonding energies 72,74 .…”

Section: Toluene and 4-methylmentioning

confidence: 99%

Insights into the Formation and Evolution of Individual Compounds in the Particulate Phase during Aromatic Photo-Oxidation

Pereira

Hamilton

Rickard

et al. 2015

Environ. Sci. Technol.

View full text Add to dashboard Cite

1Secondary organic aerosol (SOA) is well known to have adverse effects on air quality and 2 human health. However, the dynamic mechanisms occurring during SOA formation and 3 evolution are poorly understood. The time resolved SOA composition formed during the 4 photo-oxidation of three aromatic compounds, methyl chavicol, toluene and 4-methyl 5 catechol, were investigated at the European Photo-reactor. SOA was collected using a particle 6 into liquid sampler and analysed offline using state-of-the-art mass spectrometry to produce 7 temporal profiles of individual photo-oxidation products. In the photo-oxidation of methyl 8 chavicol, 70 individual compounds were characterised and three distinctive temporal profile 9 shapes were observed. The calculated mass fraction (Ci,aer/COA) of the individual SOA 10 compounds showed either a linear trend (increasing/decreasing) or exponential decay with 11 time. Substituted nitrophenols showed an exponential decay, with the nitro-group on the 12 aromatic ring found to control the formation and loss of these species in the aerosol phase. 13Nitrophenols from both methyl chavicol and toluene photo-oxidation experiments showed a 14 strong relationship with the NO2/NO (ppbv/ppbv) ratio and were observed during initial SOA 15 growth. The location of the nitrophenol aromatic substitutions was found to be critically 16 important, with the nitrophenol in the photo-oxidation of 4-methyl catechol not partitioning 17 into the aerosol phase until irradiation had stopped; highlighting the importance of studying 18 SOA formation and evolution at a molecular level.

show abstract

Phenol O–H bond dissociation energy in water clusters

Cited by 28 publications

References 27 publications

Critical Re-evaluation of the O−H Bond Dissociation Enthalpy in Phenol

Critical Re-evaluation of the O−H Bond Dissociation Enthalpy in Phenol

Energetic Differences between the Five- and Six-Membered Ring Hydrocarbons: Strain Energies in the Parent and Radical Molecules

Insights into the Formation and Evolution of Individual Compounds in the Particulate Phase during Aromatic Photo-Oxidation

Contact Info

Product

Resources

About