Structure and vibrations of the phenol-ammonia cluster

Schiefke, A.; Deusen, Ch.; Jacoby, Christoph; Gerhards, Markus; Schmitt, Michaël; Kleinermanns, Karl; Hering, P.

doi:10.1063/1.468869

Cited by 54 publications

(83 citation statements)

References 82 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The same remark also holds for the 1176 cm -1 absorption in Ph-OD. It should be noted that Schiefke et al, 7 in their HF/6-31G(d,p) calculations of phenol-ammonia complex, obtained incorrect frequency shifts for the modes involving δ(OH). As follows from the present study, a similar deficiency is noted for the HF/6-311++G(df, pd) level of calculations.…”

Section: Resultsmentioning

confidence: 99%

“…Despite extensive theoretical studies of the IR spectra of phenol reported in the past few years, [1][2][3][4][5][6][7] the assignment of several vibrations remains contradictory. Furthermore, there are still some controversies in the literature about the ability of the second-order Möller-Plesset (MP2) method to predict reliable molecular properties, vibrational frequencies, and normal coordinates of phenol, phenoxy radical, and their hydrogen-bonded complexes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

“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

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

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

show abstract

“…They appear in the R2PI spectrum of ref. [19], but they are very weak in the hole-burning spectrum shown in the same publication. For that reason, they were classified as bands from fragmentation of higher clusters.…”

Section: Phenol(nh 3 )mentioning

confidence: 85%

“…If the hole-burning spectrum shown in ref. [19] was analyzed at the high-frequency side of the origin band, [a] AE splitting, DB g , and D g constants from Humphrey et al [16] [b] Vibronic transitions from Henseler et al [15] [c] DF data from Henseler et al [15] [a] AE splitting, DB g , and D g constants from Plusquellic et al [18] [b] Vibronic transitions from Droz et al [17] [c] DF data from Droz et al [17] [a] Vibronic bands of phenol(NH 3 ) 1 from Schiefke et al [19] [b] Vibronic bands of phenol(ND 3 ) 1 from Jacoby. [20] the small intensity of the E bands in the hole-burning spectrum could easily be explained.…”

Section: Phenol(nh 3 )mentioning

confidence: 97%

See 1 more Smart Citation

Torsional Barriers in Aromatic Molecular Clusters as Probe of the Electronic Properties of the Chromophore

Jacoby

Schmitt

2004

ChemPhysChem

View full text Add to dashboard Cite

We present a computer program that is capable of fitting n-fold torsional barriers Vn (n = 2-6) and torsional constants F simultaneously to high- and low-resolution spectroscopic data of different isotopomeric internal rotors. The program has been utilized to fit independently barriers and torsional constants for both electronic states of several aromatic clusters. The constant F of the ammonia moiety in the phenol-ammonia cluster is shown to decrease upon electronic excitation, thus imaging the formation of a hydrogen-bonded complex between the phenoxy radical and the NH4 radical in the excited state. In contrast, for the naphthol-ammonia 1:1 clusters no change of F of ammonia could be found. For phenol-methanol cluster we found a decrease of F upon excitation which points to a stronger hydrogen bond between phenol and methanol in the excited state. A strong reduction of the torsional barrier upon excitation points to the formation of a methoxonium radical in a similar photoreaction as in phenol-ammonia cluster. For the phenol-water system we postulate the same mechanism, a photoreaction, which leads to a translocated hydrogen atom in the S1 state what can be deduced from the change of the torsional constant upon electronic excitation.

show abstract

General and Theoretical Aspects of Phenols

Nguyen

Kryachko

Vanquickenborne

2009

Patai's Chemistry of Functional Groups

View full text Add to dashboard Cite

Introduction Molecular Structure and Bonding of Phenol Structures and Properties of Substituted Phenols Energetics of some Fundamental Processes Hydrogen Bonding Abilities of Phenols Open Theoretical Problems Acknowledgements

show abstract

Structure and vibrations of the phenol-ammonia cluster

Cited by 54 publications

References 82 publications

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

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

Torsional Barriers in Aromatic Molecular Clusters as Probe of the Electronic Properties of the Chromophore

General and Theoretical Aspects of Phenols

Contact Info

Product

Resources

About