The vibrational spectrum and torsion of phenol

“…There is an interaction between the delocalised electrons in the benzene ring and one of the lone pairs on the oxygen atom which makes the ring much more reactive than it is in benzene itself. The structure and vibrational frequencies of phenol have been the subject of many experimental [38][39][40][41] and theoretical studies [42,43].…”

Section: Phenolmentioning

confidence: 99%

Studies on m-benzyne and phenol via improved virtual orbital-complete active space configuration interaction (IVO-CASCI) analytical gradient method

Chattopadhyay

Chaudhuri

Mahapatra³

2010

Chemical Physics Letters

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“…This vibration has also been obtained by other DFT calculations [93,95,96,98,113]. Despite of some C-C stretch character, this vibration has C-H and O-H in-plane bending character and has been assigned to a strong band at 1177 cm −1 in the IR spectrum of phenol vapor [114,115].…”

Section: Ir Spectra: Comparison Of Calculated To Experimental Resultsmentioning

confidence: 70%

Electronic and Molecular Structures of Heteroradialenes: A Combined Synthetic, Computational, Spectroscopic, and Structural Study Identifying IR Spectroscopy as a Simple but Powerful Experimental Probe

Richthofen

Feldscher

Lippert

et al. 2013

Zeitschrift Für Naturforschung B

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The vicinity of a hydrogen bond donor (O-H) and a hydrogen bond acceptor (C=O or C=N-R) in salicylaldehydes and ortho-Schiff bases results in significant structural variations compared to the monosubstituted derivatives that are reflected in the electronic structure and thus in the spectroscopic properties. This interplay between intramolecular hydrogen bonding and multicenter π-electron delocalization is the origin of the concept of resonance-assisted hydrogen bonding (RAHB). Herein, the complexity is extended from one hydrogen bond donor-acceptor pair in salicylaldehyde and ortho-Schiff bases to three hydrogen bond donor-acceptor pairs in 2,4,6-tricarbonyl-and 2,4,6-triimine-substituted phloroglucinols (1,3,5-trihydroxybenzene), respectively. To evaluate the changes in the molecular and electronic structures, we have performed a comprehensive computational, spectroscopic, and structural study starting from monosubstituted benzene derivatives as references over ortho-disubstituted derivates to the sixfold-substituted derivatives. Whereas in salicylaldehydes, ortho-Schiff bases, and 2,4,6-tricarbonyl-phloroglucinols the phenolic O-protonated tautomers represent the energy minima, the N-protonated tautomers represent the energy minima in 2,4,6-triiminephloroglucinols. The analysis provides a keto-enamine resonance structure with six exocyclic double bonds to be dominant for these species reminiscent of [6]radialenes, which were termed heteroradialenes. These heteroradialenes are non-aromatic alicycles. However, the predominance of this resonance structure does not represent a sudden change going from the 2,4,6-tricarbonyl-to the 2,4,6-triimine-phloroglucinols, but a gradual increase of analogous resonance structure contributions is observed even in salicylaldehyde and ortho-Schiff bases demonstrating some hetero-orthoquinodimethane character. These changes are, besides in the molecular structures, well reflected in the IR spectra, which can therefore be used as a simple tool to probe the electronic structures in these systems. Interruption of the delocalized π system supporting the intramolecular hydrogen bond, i. e. going from 2,4,6-triimine-to 2,4,6-triamine-substituted phloroglucinols, reestablishes an O-protonated aromatic phloroglucinol system.

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“…Therefore the calculated frequencies were scaled by fitting these frequencies with a linear least square fit to the experimental values of bare phenol [ 19] and bare methanol [20]. The scaling factors obtained for the phenol and methanol frequencies are 0.9032 and 0.8992, respectively.…”

Section: B Intramoleeular Vibrationsmentioning

confidence: 99%

Vibrational analysis of phenol/(methanol)1

Gerhards

Beckmann

Kleinermanns

1994

Z Phys D - Atoms, Molecules and Clusters

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Abstract. Ab initio calculations at the Hartree-Fock 4-31G* level were performed in order to calculate binding energies and vibrational frequencies of the phenol/ CH3OH-cluster and two deuterated isotopomers (d-phenol/CH3OD, d-phenol-CD3OD ). The minimum energy structure is trans-linear, as for the phenol/H20-cluster. The calculated frequencies of phenol and methanol as well as the intramolecular frequencies of the phenol/ CH3OH-cluster are assigned to experimental values. The calculated intermolecular frequencies of the phenol/ CH3OH-cluster are compared with the available experimental frequencies of the So (and S0-state of the phenol/ methanol-cluster and the similar p-cresol/methanol-cluster. Assignments are suggested for the a and pl-mode. In order to clarify the assignment of the low frequency vibration at 22 cm -1 anharmonic corrections for the/?2-mode of the phenol/CH3OH-cluster are calculated. These calculations show only slight anharmonicity compared with the/?2-mode calculations carried out for the phenol/ H20-cluster.

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The vibrational spectrum and torsion of phenol

Cited by 220 publications

References 10 publications

Studies on m-benzyne and phenol via improved virtual orbital-complete active space configuration interaction (IVO-CASCI) analytical gradient method

Studies on m-benzyne and phenol via improved virtual orbital-complete active space configuration interaction (IVO-CASCI) analytical gradient method

Electronic and Molecular Structures of Heteroradialenes: A Combined Synthetic, Computational, Spectroscopic, and Structural Study Identifying IR Spectroscopy as a Simple but Powerful Experimental Probe

Vibrational analysis of phenol/(methanol)1

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