Spectroscopy

Duncan, A B F

doi:10.1146/annurev.pc.05.100154.001153

Cited by 5 publications

(10 citation statements)

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“…As noted before, 12,15 single-photon IRPD may be limited by bond energies or the rate of intramolecular vibrational relaxation ͑IVR͒. The bond energy of V ϩ (H 2 O) (12 280 cm Ϫ1 ) 4,5 is too high for single photon IRPD in the OH stretch fundamentals.…”

Section: Infrared Spectroscopy Of V ¿mentioning

confidence: 99%

“…11 Our group has recently applied IRPD to transition metal ion complexes. [12][13][14][15] Here, we investigate transition metal cation-water complexes for the first time in a study of V ϩ (H 2 O) and V ϩ (D 2 O).…”

Section: Infrared Spectroscopy Of V ¿mentioning

confidence: 99%

“…Ions are mass selected and fragments are analyzed with a reflectron time-of-flight spectrometer. 7,12,15 IR excitation near the O-H (3500-3800 cm Ϫ1 ) and O-D (2600-2800 cm Ϫ1 ) stretches employs a LaserVision optical parametric oscillator/amplifier ͑OPO/OPA; linewidthϳ0.3 cm Ϫ1 ) pumped by a Continuum 9010 Nd:YAG laser. Mass spectra recorded with a LeCroy LT-341 digital oscilloscope yield fragment ion-versus-energy photodissociation spectra.…”

Section: Infrared Spectroscopy Of V ¿mentioning

confidence: 99%

“…Multiphoton dissociation is possible, but its efficiency may be limited by state densities and IVR. We therefore use ''argon tagging'' 11͑d͒, 12,15,[19][20][21][22][23] to achieve more efficient photodissociation. This ensures that complexes are cold and allows dissociation without large perturbations on the spectrum (Ͻ10 cm Ϫ1 shifts are typical with/without argon͒.…”

Section: Infrared Spectroscopy Of V ¿mentioning

confidence: 99%

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Infrared spectroscopy of V+(H2O) and V+(D2O) complexes: Solvent deformation and an incipient reaction

Walker¹,

Walters²,

Pillai³

et al. 2003

The Journal of Chemical Physics

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V + ( H 2 O ) Ar n and V+(D2O)Arn complexes are studied with mass-selected infrared photodissociation spectroscopy in the O–H (O–D) stretch region. Two vibrational bands are measured 50–80 cm−1 to the red from the symmetric and asymmetric stretches in free water. Rotational analysis for V+(H2O)Ar indicates a C2v geometry with argon opposite water and significant expansion of the H–O–H angle. The v=1 level in the asymmetric stretch undergoes distortion consistent with selective excitation into the coordinate of an insertion reaction.

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Section: Infrared Spectroscopy Of V ¿mentioning

confidence: 99%

Section: Infrared Spectroscopy Of V ¿mentioning

confidence: 99%

Section: Infrared Spectroscopy Of V ¿mentioning

confidence: 99%

Section: Infrared Spectroscopy Of V ¿mentioning

confidence: 99%

See 2 more Smart Citations

Infrared spectroscopy of V+(H2O) and V+(D2O) complexes: Solvent deformation and an incipient reaction

Walker¹,

Walters²,

Pillai³

et al. 2003

The Journal of Chemical Physics

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“…[1][2][3][4][5][6][7][8][9] Such solvation effects are particularly important for charged species, because of the larger strength and longer range of ion-solvent interactions compared to corresponding neutral-neutral interactions. [9][10][11][12][13][14][15] Biological molecules are often ͑locally͒ charged due to either ͑de͒protonation or charge separation. Moreover, many fundamental chemical reaction mechanisms are ion-molecule reactions, and their properties strongly depend on solvation due to large forces between the ionic species and the solvent molecules.…”

Section: Introductionmentioning

confidence: 99%

IR signature of the photoionization-induced hydrophobic→hydrophilic site switching in phenol-Arn clusters

Ishiuchi

Sakai

Tsuchida

et al. 2007

The Journal of Chemical Physics

139

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IR spectra of phenol-Arn (PhOH-Arn) clusters with n=1 and 2 were measured in the neutral and cationic electronic ground states in order to determine the preferential intermolecular ligand binding motifs, hydrogen bonding (hydrophilic interaction) versus pi bonding (hydrophobic interaction). Analysis of the vibrational frequencies of the OH stretching motion, nuOH, observed in nanosecond IR spectra demonstrates that neutral PhOH-Ar and PhOH-Ar2 as well as cationic PhOH+-Ar have a pi-bound structure, in which the Ar atoms bind to the aromatic ring. In contrast, the PhOH+-Ar2 cluster cation is concluded to have a H-bound structure, in which one Ar atom is hydrogen-bonded to the OH group. This pi-->H binding site switching induced by ionization was directly monitored in real time by picosecond time-resolved IR spectroscopy. The pi-bound nuOH band is observed just after the ionization and disappears simultaneously with the appearance of the H-bound nuOH band. The analysis of the picosecond IR spectra demonstrates that (i) the pi-->H site switching is an elementary reaction with a time constant of approximately 7 ps, which is roughly independent of the available internal vibrational energy, (ii) the barrier for the isomerization reaction is rather low(<100 cm(-1)), (iii) both the position and the width of the H-bound nuOH band change with the delay time, and the time evolution of these spectral changes can be rationalized by intracluster vibrational energy redistribution occurring after the site switching. The observation of the ionization-induced switch from pi bonding to H bonding in the PhOH+-Ar2 cation corresponds to the first manifestation of an intermolecular isomerization reaction in a charged aggregate.

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Thermally Activated vs. Photochemical Hydrogen Evolution Reactions–A Tale of Three Metals

Ončák

Siu

Linde

et al. 2023

Chemistry A European J

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Molecular processes behind hydrogen evolution reactions can be quite complex. In macroscopic electrochemical cells, it is extremely difficult to elucidate and understand their mechanism. Gas phase models, consisting of a metal ion and a small number of water molecules, provide unique opportunities to understand the reaction pathways in great detail. Hydrogen evolution in clusters consisting of a singly charged metal ion and one to on the order of 50 water molecules has been studied extensively for magnesium, aluminum and vanadium. Such clusters with around 10-20 water molecules are known to eliminate atomic or molecular hydrogen upon mild activation by room temperature blackbody radiation. Irradiation with ultraviolet light, by contrast, enables hydrogen evolution already with a single water molecule. Here, we analyze and compare the reaction mechanisms for hydrogen evolution on the ground state as well as excited state potential energy surfaces. Five distinct mechanisms for evolution of atomic or molecular hydrogen are identified and characterized.

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Spectroscopy

Cited by 5 publications

References 0 publications

Infrared spectroscopy of V+(H2O) and V+(D2O) complexes: Solvent deformation and an incipient reaction

Infrared spectroscopy of V+(H2O) and V+(D2O) complexes: Solvent deformation and an incipient reaction

IR signature of the photoionization-induced hydrophobic→hydrophilic site switching in phenol-Arn clusters

Thermally Activated vs. Photochemical Hydrogen Evolution Reactions–A Tale of Three Metals

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