Electronic spectroscopy of 1-naphthol/solvent clusters 1-NpOH/S, S = H2O, Ar and N2

Zierhut, M.; Roth, Wolfgang R.; Dümmler, Stefan; Fischer, Ingo

doi:10.1016/j.chemphys.2004.06.041

Cited by 18 publications

(31 citation statements)

References 54 publications

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“…In the dispersively bound 1NpOH•S complexes where S is a noble-gas or N 2 , the atoms or the N 2 molecule is adsorbed to the Face of the naphthol aromatic system and the spectral shifts are small, between δν = −2 cm −1 for S = Ne and −35 cm −1 for S = Xe. 37,53 Similarly, the Face isomer of 1NpOH•cyclopropane exhibits a small spectral blue shift of δν = +2 cm −1 , 35,38 for 1NpOH•cyclohexane δν = −1.7 cm −1 , and for the cycloheptane complex isomers A and B the shifts are δν = −38.5 and −32.9 cm −1 , close to that of the Xe complex. 35,38 If the admolecule is H-bonded to the −OH group of 1-naphthol OH group, as in the H 2 O, CH 3 OH, and NH 3 complexes, the spectral red shifts are much larger, being δν = −145, −158, and −236 cm −1 , respectively, 33,34 and the H-bonded Edge isomer of 1NpOH•cyclopropane has a redshift of δν = −72 cm −1 .…”

Section: A Structures Of the 1-naphthol•n-alkane Complexes And Spectmentioning

confidence: 85%

Intermolecular dissociation energies of 1-naphthol·n-alkane complexes

Knochenmuss

Maity

Balmer

et al. 2018

The Journal of Chemical Physics

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Using the stimulated-emission-pumping/resonant 2-photon ionization (SEP-R2PI) method, we have determined accurate intermolecular dissociation energies D of supersonic jet-cooled intermolecular complexes of 1-naphthol (1NpOH) with alkanes, 1NpOH·S, with S = methane, ethane, propane, and n-butane. Experimentally, the smaller alkanes form a single minimum-energy structure, while 1-naphthol·n-butane forms three different isomers. The ground-state dissociation energies D(S) for the complexes with propane and n-butane (isomers A and B) were bracketed within ±0.5%, being 16.71 ± 0.08 kJ/mol for S = propane and 20.5 ± 0.1 kJ/mol for isomer A and 20.2 ± 0.1 kJ/mol for isomer B of n-butane. All 1NpOH·S complexes measured previously exhibit a clear dissociation threshold in their hot-band detected SEP-R2PI spectra, but weak SEP-R2PI bands are observed above the putative dissociation onset for the methane and ethane complexes. We attribute these bands to long-lived complexes that retain energy in rotation-type intermolecular vibrations, which couple only weakly to the dissociation coordinates. Accounting for this, we find dissociation energies of D(S) = 7.98 ± 0.55 kJ/mol (±7%) for S = methane and 14.5 ± 0.28 kJ/mol (±2%) for S = ethane. The D values increase by only 1% upon S → S excitation of 1-naphthol. The dispersion-corrected density functional theory methods B97-D3, B3LYP-D3, and ωB97X-D predict that the n-alkanes bind dispersively to the naphthalene "Face." The assignment of the complexes to Face structures is supported by the small spectral shifts of the S → S electronic origins, which range from +0.5 to -15 cm. Agreement with the calculated dissociation energies D(S) is quite uneven, the B97-D3 values agree within 5% for propane and n-butane, but differ by up to 20% for methane and ethane. The ωB97X-D method shows good agreement for methane and ethane but overestimates the D(S) values for the larger n-alkanes by up to 20%. The agreement of the B3LYP-D3 D values is intermediate between the other two methods.

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Section: A Structures Of the 1-naphthol•n-alkane Complexes And Spectmentioning

confidence: 85%

Intermolecular dissociation energies of 1-naphthol·n-alkane complexes

Knochenmuss

Maity

Balmer

et al. 2018

The Journal of Chemical Physics

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“…In this work, we report the first comparative analysis of the mechanisms of excited state deactivation of two prototypical photochemical systems: 1‐naphthol ( 1 ) and 2‐naphthol ( 2 ) as well as of their microsolvated water clusters. Numerous studies of isolated 1 and 2 , as well as their clusters with H 2 O (D 2 O), and NH 3 revealed complex excited state dynamics. Specifically, there exists a strong dependence on the isomer and solvent, as well as on the size and geometry of the cluster.…”

Section: Introductionmentioning

confidence: 99%

Photochemistry of 1‐ and 2‐Naphthols and Their Water Clusters: The Role of ¹ππ*(L_a) Mediated Hydrogen Transfer to Carbon Atoms

Novak

Prlj

Basarić

et al. 2017

Chemistry A European J

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The computational analysis of the isomer- and conformer-dependent photochemistry of 1- and 2-naphthols and their microsolvated water clusters is motivated by their very different excited state reactivities. We present evidence that 1- and 2-naphthol follow distinct excited state deactivation pathways. The deactivation of 2-naphthols, 2-naphthol water clusters, as well as of the anti conformer of 1-naphthol is mediated by the optically dark πσ* state. The dynamics of the πσ* surface leads to the homolytic cleavage of the OH bond. On the contrary, the excited state deactivation of syn 1-naphthol and 1-naphthol water clusters follows an uncommon reaction pathway. Upon excitation to the bright ππ*(L ) state, a highly specific excited state hydrogen transfer (ESHT) to carbon atoms C8 and C5 takes place, yielding 1,8- and 1,5-naphthoquinone methides. The ESHT pathway arises from the intrinsic electronic properties of the ππ*(L ) state of 1-naphthols.

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“…28 In the 1NpOH·Ar and 1NpOH·N 2 complexes the interaction is dominantly or purely dispersive, the Ar or N 2 moiety is adsorbed on the aromatic face of 1NpOH, and the experimental spectral shifts are small, δν = −15 cm −1 and −14 cm −1 , respectively. 43 Similarly, the face isomer of 1NpOH·cyclopropane exhibits a small spectral shift to the blue, δν = +2 cm −1 . 28 In contrast, the spectral shifts are always to the red and larger if the solvent molecule is H-bonded to the naphthol OH group, as in the complexes 25,27,32 The nonclassically H-bonded edge isomer of 1NpOH·cyclopropane exhibits a red shift of −71.5 cm −1 , about half that of the 1NpOH·H 2 O complex.…”

Section: A Complex Structures and Spectral Shiftsmentioning

confidence: 99%

Intermolecular dissociation energies of dispersively bound 1-naphthol⋅cycloalkane complexes

Maity

Ottiger

Balmer

et al. 2016

The Journal of Chemical Physics

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Electronic spectroscopy of 1-naphthol/solvent clusters 1-NpOH/S, S = H2O, Ar and N2

Cited by 18 publications

References 54 publications

Intermolecular dissociation energies of 1-naphthol·n-alkane complexes

Intermolecular dissociation energies of 1-naphthol·n-alkane complexes

Photochemistry of 1‐ and 2‐Naphthols and Their Water Clusters: The Role of ¹ππ*(L_a) Mediated Hydrogen Transfer to Carbon Atoms

Intermolecular dissociation energies of dispersively bound 1-naphthol⋅cycloalkane complexes

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Electronic spectroscopy of 1-naphthol/solvent clusters 1-NpOH/S, S = H2O, Ar and N2

Cited by 18 publications

References 54 publications

Intermolecular dissociation energies of 1-naphthol·n-alkane complexes

Intermolecular dissociation energies of 1-naphthol·n-alkane complexes

Photochemistry of 1‐ and 2‐Naphthols and Their Water Clusters: The Role of 1ππ*(La) Mediated Hydrogen Transfer to Carbon Atoms

Intermolecular dissociation energies of dispersively bound 1-naphthol⋅cycloalkane complexes

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Photochemistry of 1‐ and 2‐Naphthols and Their Water Clusters: The Role of ¹ππ*(L_a) Mediated Hydrogen Transfer to Carbon Atoms