High resolution UV spectroscopy of phenol and the hydrogen bonded phenol-water cluster

Berden, Giel; Meerts, W. Leo; Schmitt, Michaël; Kleinermanns, Karl

doi:10.1063/1.470821

Cited by 244 publications

(242 citation statements)

References 49 publications

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“…Comparing these results for the dynamics with other aromatic water clusters like phenol-water we found that BZNW decays faster upon clustering, whereas phenol-water has a longer lifetime than pure phenol [6]. This may be due to the different nonradiative processes responsible for the dynamics in the two systems.…”

Section: B) Analysis Of the Uv Spectramentioning

confidence: 61%

“…The bonding distance is expected to affirm the character of the bonding. The main contribution is from hydrogen bonding, but due to the large permanent dipole moment of BZN of 4.18 debye [16] an influence of the dipole-dipole interaction on the bonding is expected different from the hydrogen bonding recently investigated in phenol-water [6] and pyridone-water [8].…”

Section: Introductionmentioning

confidence: 99%

“…The bond length of ro = 2.477(4) A is between the typical bond length of a van der Waals bonded (e. g. van der Waals bond length of BZN-Ar in So (Si): 3.598 A (3.52 A) [3,4]) and a hydrogen-bonded system (e. g. phenol-water: the distance from the phenol's hydrogen to the water's oxygen in So (Si) is roughly 1.97 A (1.93 A) [6]). The two links of the water to the ortho hydrogen and the C-N group should be compared to recent findings in pyridone-water.…”

Section: C) Cluster Structurementioning

confidence: 99%

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Combined High Resolution UV and Microwave Results: Structure of the Benzonitrile•Water Complex

Helm

Vogel

Neusser

et al. 1997

Zeitschrift Für Naturforschung A

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High resolution ultraviolet (UV) and molecular beam Fourier transform microwave (MB FTMW) spectroscopy of the benzonitrile-water (BZNW) cluster were performed to measure cluster structures in the So and Si states. The MW experiments provide additional information on the structure and the 14 N-nuclear quadrupole coupling in the ground state So, the UV experiments on the dynamics in Si.The rotationally resolved sub-Doppler UV spectra of BZNW were measured by mass-selective resonance-enhanced two-photon ionization. For the first time this UV technique has been applied to hydrogen-bonded clusters. From the UV spectra the rotational constants are obtained by Correlation Automated Rotational Fitting. The MW spectra were analyzed with the model of a centrifugally distorted rotor including nuclear quadrupole coupling. A r 0 -fit of the water position within the cluster is performed. The water is found to be located with its oxygen nearly in the plane of benzonitrile (BZN). For So (Si), the distance of the oxygen to the ortho hydrogen is r 0 = 2.477(4) Ä (2.457(2) A) and the angle to the ortho carbon-hydrogen bond 143.34(2)° (141.91(3)°). The structure differences in Si and So can be explained by the structure changes of the BZN molecule. A line broadening, which points to a faster decay in Si upon clustering with the polar solvent, is observed for the BZNW cluster.

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Section: B) Analysis Of the Uv Spectramentioning

confidence: 61%

Section: Introductionmentioning

confidence: 99%

Section: C) Cluster Structurementioning

confidence: 99%

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Combined High Resolution UV and Microwave Results: Structure of the Benzonitrile•Water Complex

Helm

Vogel

Neusser

et al. 1997

Zeitschrift Für Naturforschung A

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“…(s = 1)'' was determined to be 25 455(10) MHz by Berden et al by using rotationally resolved UV spectroscopy. [34] No information on the first-order perturbation coefficients is available from a twofold potential because of the lack of degenerate levels in this case. The second-order perturbation coefficients can be obtained from the difference of the rotational constants of (s = 0) and (s = 1) levels.…”

Section: Phenol(h 2 O)mentioning

confidence: 99%

“…[a] Experimental torsional splitting and DB g from Berden et al [34] [b] Torsional bands from Schmitt et al [35] [c] DF from ref. [36].…”

Section: Phenol(h 2 O)mentioning

confidence: 99%

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

Jacoby

Schmitt

2004

ChemPhysChem

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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.

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Vibrational Energy Relaxation Dynamics of XH Stretching Vibrations of Aromatic Molecules in the Electronic Excited State

Ebata

2010

Hydrogen Bonding and Transfer in the Excited State

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The vibrational energy relaxation (VER) of polyatomic molecules has been the central issue in many of the chemical reactions in condensed phase [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] as well as in gas phase . The vibrational energy introduced to the molecule is immediately redistributed within the molecule or to the surrounding molecules. Among many vibrations investigated, the VER of the OH and NH stretching vibrations may be most important from the viewpoint of understanding the dynamics of the H-bonding of protic solvent molecules as well as biologically relevant molecules [42][43][44][45][46][47][48]. VER of the electronically excited OH stretching vibration of aromatic molecules and their hydrogen-bonded cluster is especially interesting. Most of the aromatic molecules having an OH group become more acidic upon electronic excitation, leading to hydrogen/proton transfer reactions [49][50][51][52][53][54][55][56][57][58][59][60][61][62]. We expect that vibrational excitation may lead to additional effects.In this review, we report the study of the intramolecular and intracluster vibrational energy redistribution (IMVR and ICVR), vibrational predissociation (VP) and isomerization of molecules and their clusters in the S 1 state by using UV-IR double-resonance (DR) spectroscopy (Figure 2.1) [63][64][65][66][67]. In this spectroscopy, the molecule or the cluster in a supersonic jet is excited to the zero-point level of S 1 by UV laser light, and is further excited to the XH stretch vibrational level by a tunable IR laser light. VER of vibrationally excited molecules and clusters is observed by dispersed fluorescence spectroscopy. After the UV-IR DR excitation to the XH stretch level, the molecule or the cluster emits a broad fluorescence in a wide energy region owing to fast IMVR or ICVR. If the internal energy is high enough to break the cluster, it dissociates by VP and emission of the fragment is observed. We can distinguish these processes by measuring the dispersed

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High resolution UV spectroscopy of phenol and the hydrogen bonded phenol-water cluster

Cited by 244 publications

References 49 publications

Combined High Resolution UV and Microwave Results: Structure of the Benzonitrile•Water Complex

Combined High Resolution UV and Microwave Results: Structure of the Benzonitrile•Water Complex

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

Vibrational Energy Relaxation Dynamics of XH Stretching Vibrations of Aromatic Molecules in the Electronic Excited State

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