A new detection scheme for synchronous, high resolution ZEKE and MATI spectroscopy demonstrated on the Phenol·Ar complex

Dessent, Caroline E. H.; Haines, Stephen R.; Müller‐Dethlefs, Klaus

doi:10.1016/s0009-2614(99)01193-8

Cited by 110 publications

(135 citation statements)

References 15 publications

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“…28 This shift is almost twice the red-shift for the phenol + Á Á ÁAr(p) dimer (DIE = À176 cm À1 ). 17 This observation indicates the similarity of the intermolecular bonding type in phenol (+) Á Á ÁAr(p) and phenol (+) Á Á ÁAr 2 (2p). This relationship reflects the same trend as already observed in the case of aniline (+) Á Á ÁAr n (np) 7 and fluorobenzene (+) Á Á ÁAr n (np) 5 with n r 2, where the additivity rule also holds almost strictly, DIE = À111 (n = 1) and À219 (n = 2) cm À1 for aniline, and DIE = À223 (n = 1) and À422 (n = 2) cm À1 for fluorobenzene.…”

Section: Ionization Energymentioning

confidence: 78%

Mass analyzed threshold ionization spectra of phenol⋯Ar₂: ionization energy and cation intermolecular vibrational frequencies

Armentano

Tong

Riese

et al. 2011

Phys. Chem. Chem. Phys.

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The phenol + Á Á ÁAr 2 complex has been characterized in a supersonic jet by mass analyzed threshold ionization (MATI) spectroscopy via different intermediate intermolecular vibrational states of the first electronically excited state (S 1 ). From the spectra recorded via the S 1 0 0 origin and the S 1 b x intermolecular vibrational state, the ionization energy (IE) has been determined as 68 288 AE 5 cm À1 , displaying a red shift of 340 cm À1 from the IE of the phenol + monomer. Well-resolved, nearly harmonic vibrational progressions with a fundamental frequency of 10 cm À1 have been observed in the ion ground state (D 0 ) and assigned to the symmetric van der Waals (vdW) bending mode, b x , along the x axis containing the C-O bond. MATI spectra recorded via the S 1 state involving other higher-lying intermolecular vibrational states (s 1 s , b 3 x , s 1 s b 1 x , s 1 s b 2 x ) are characterized by unresolved broad structures.

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Section: Ionization Energymentioning

confidence: 78%

Mass analyzed threshold ionization spectra of phenol⋯Ar₂: ionization energy and cation intermolecular vibrational frequencies

Armentano

Tong

Riese

et al. 2011

Phys. Chem. Chem. Phys.

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“…[19][20][21][22][26][27][28] Tunable UV exc/ion laser pulses are generated by frequency doubling of outputs of two Nd:YAGpumped dye lasers (Radiant Dyes: Narrow scan, Continuum: Surelite 10). Tunable IR laser radiation is obtained from the idler output of an IR optical parametric oscillator (LaserVision).…”

Section: Methodsmentioning

confidence: 99%

“…The interpretation of barrierless p -H isomerization derived from the IR spectra is in apparent conflict with the interpretation derived from the ZEKE and MATI spectroscopies and also with theoretical studies that predict a barrier height larger than 100 cm À1 . 14,15,[18][19][20][21][22] The analysis of the ZEKE and MATI spectra strongly suggests that there is no dynamics between the p-and H-bound minima. In contrast, the time-resolved IR spectra clearly illustrate the p -H isomerization.…”

Section: Introductionmentioning

confidence: 99%

Mass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol–Ar cluster near the ionization threshold

Miyazaki

Yoshikawa

Michels

et al. 2015

Phys. Chem. Chem. Phys.

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The structure of the phenol-argon cluster (PhOH-Ar) in high-n Rydberg states is investigated by the newly developed technique of mass analyzed threshold ionization detected infrared (MATI-IR) spectroscopy. This method selectively measures IR spectra of molecular clusters in very high-n Rydberg states (n 4 100) utilized in zero kinetic energy (ZEKE) photoelectron and MATI spectroscopy, whose ionic cores are essentially the same as the corresponding bare cation. The MATI-IR spectrum exhibits only the free OH stretching vibration (n p OH ) when the p-bound cluster of the neutral ground electronic state (S 0 ) is resonantly excited via the S 1 origin to Rydberg states converging to its adiabatic ionization energy level, IE 0 (p). When Rydberg states converging to vibrationally excited levels of the local p-bound minimum are prepared, in addition to n p OH also the hydrogen-bonded OH stretching vibration (n H OH ) of the H-bonded global minimum is observed in the MATI-IR spectra, even for vibrational excitation of only 14 cm À1 above IE 0 (p). These results show that the p -H site switching reaction of the Ar ligand from the aromatic ring to the OH group proceeds only from vibrationally excited states in the p-bound cation core with a small barrier of less than 14 cm À1 from IE 0 (p). On the other hand, directly photoionized PhOH + -Ar shows both n H OH and n p OH in the IR spectra, even when it is just ionized to IE 0 (p). This result implies that the ionizationinduced p -H site switching occurs without excess energy in the H-bound or p-bound cations, in contrast to very high-n Rydberg states converging to levels of the p-bound cation. The different efficiencies of the site switching for the Rydberg ion core and the bare ion and the mechanism for the p -H site switching are interpreted by direct ionization from the p-bound to the H-bound structures in addition to the conventional vertical ionization and transitions to high-n Rydberg states.

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“…The pulsed field ionization of a ZEKE Rydberg state produces both an electron and an ion. When this electron is measured we call this method zero electron kinetic energy (ZEKE) photoelectron spectroscopy; when the corresponding ion is selectively measured, we call this mass-selected ZEKE, or mass-analyzed threshold ionization (MATI) 10,[101][102][103] . Since the motion of the Rydberg electron is completely decoupled from the internal motion of the ion core, a ZEKE spectrum results in the observation of vibrational and rotational structure of the corresponding molecular cation.…”

Section: Mass-resolved Zeke Spectroscopymentioning

confidence: 99%

“…In terms of spectral resolution, the MATI resolution can be better than 0.1 cm -1 (ref. 103 ), and ZEKE and MATI are fully equivalent 10,106 . For the phenol...argon complex, Fig.…”

Section: Mass-resolved Zeke Spectroscopymentioning

confidence: 99%

The World of Non-Covalent Interactions: 2006

Hobza¹,

Zahradník²,

Müller‐Dethlefs³

2006

Collect. Czech. Chem. Commun.

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247

235

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The review focusses on the fundamental importance of non-covalent interactions in nature by illustrating specific examples from chemistry, physics and the biosciences. Laser spectroscopic methods and both ab initio and molecular modelling procedures used for the study of non-covalent interactions in molecular clusters are briefly outlined. The role of structure and geometry, stabilization energy, potential and free energy surfaces for molecular clusters is extensively discussed in the light of the most advanced ab initio computational results for the CCSD(T) method, extrapolated to the CBS limit. The most important types of non-covalent complexes are classified and several small and medium size non-covalent systems, including H-bonded and improper H-bonded complexes, nucleic acid base pairs, and peptides and proteins are discussed with some detail. Finally, we evaluate the interpretation of experimental results in comparison with state of the art theoretical models: this is illustrated for phenol...Ar, the benzene dimer and nucleic acid base pairs. A review with 270 references.

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A new detection scheme for synchronous, high resolution ZEKE and MATI spectroscopy demonstrated on the Phenol·Ar complex

Cited by 110 publications

References 15 publications

Mass analyzed threshold ionization spectra of phenol⋯Ar₂: ionization energy and cation intermolecular vibrational frequencies

Mass analyzed threshold ionization spectra of phenol⋯Ar₂: ionization energy and cation intermolecular vibrational frequencies

Mass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol–Ar cluster near the ionization threshold

The World of Non-Covalent Interactions: 2006

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A new detection scheme for synchronous, high resolution ZEKE and MATI spectroscopy demonstrated on the Phenol·Ar complex

Cited by 110 publications

References 15 publications

Mass analyzed threshold ionization spectra of phenol⋯Ar2: ionization energy and cation intermolecular vibrational frequencies

Mass analyzed threshold ionization spectra of phenol⋯Ar2: ionization energy and cation intermolecular vibrational frequencies

Mass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol–Ar cluster near the ionization threshold

The World of Non-Covalent Interactions: 2006

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Mass analyzed threshold ionization spectra of phenol⋯Ar₂: ionization energy and cation intermolecular vibrational frequencies

Mass analyzed threshold ionization spectra of phenol⋯Ar₂: ionization energy and cation intermolecular vibrational frequencies