Photofragmentation of mass-selected ICl−(CO2)<i>n</i> cluster ions: Solvation effects on the structure and dynamics of the ionic chromophore

Nadal, Maria E.; Kleiber, P. D.; Lineberger, W. C.

doi:10.1063/1.471904

Cited by 68 publications

(53 citation statements)

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“…Heteronuclear dihalides have not been neglected, however, and they pose some distinct challenges. In 1996, Nadal, Kleiber, and Lineberger 21, 22 measured the photofragmentation products from ICl -and ICl -(CO 2 ) n clusters following excitation at 644 nm ( Figure 1). Excitation of the bare ion to the A′ ( 2 II 1/2 ) state leads exclusively to the formation of iodide (I -) ions and chlorine (Cl) atoms ( Figure 2).…”

Section: Introductionmentioning

confidence: 99%

“…Solvent Effects on the Electronic Absorption Spectrum. Nadal, Kleiber, and Lineberger 21, 22 have measured the effect of clustering on the ICl -electronic absorption in the red region of the spectrum. In ICl -(CO 2 ) 4 , the only cluster size studied, they found a small red shift of ∼10 nm in the A′ r X absorption band near 700 nm.…”

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confidence: 99%

“…Figure 10 shows the average number of solvent molecules lost for each experimental channel. 22 The Cl --based products lose, on average, only one or two CO 2 molecules out to cluster sizes as large as n ) 10. To produce the same Cl -fragments with the ground-state I atom would require dissipation of a minimum of 700 meV additional energy.…”

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confidence: 99%

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Experiments on the photodissociation of ICl -within size-selected CO 2 clusters [Nadal, M. E.;Kleiber, P. D.; Lineberger, W. C. J. Chem. Phys.

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confidence: 99%

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Simulations of ICl⁻(CO₂)_nPhotodissociation: Effects of Structure, Excited State Charge Flow, and Solvent Dynamics

Faeder

Parson

2009

J. Phys. Chem. A

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Experiments on the photodissociation of ICl(-) within size-selected CO(2) clusters [Nadal, M. E.; Kleiber, P. D.; Lineberger, W. C. J. Chem. Phys. 1996, 105, 504.] differ from analogous experiments on homonuclear systems in two major ways: an early onset of caged, ICl(-)-based products with cluster size peaking at n = 5 and a rapid decline of caging after n = 5 in favor of dissociated, Cl(-)-based fragments. Using an effective Hamiltonian model for the solute electronic structure and nonadiabatic MD trajectories, we have simulated the photodissociation of these clusters and found good agreement between experimental and simulated product distributions. The strong preference of the solvent for chlorine in the initial cluster structure, along with favorable kinematics, leads to the efficient caging at small n. At all cluster sizes, the Cl(-)-based fragments are formed by an adiabatic process and are accompanied by spin-orbit excited iodine. Caging of ICl(-) also occurs on the excited state potential surface, and electronic relaxation is not observed during the 100 ps trajectories. For n > 5, the initially caged products appear to be metastable, decaying to solvent-separated Cl(-)...I pairs that subsequently dissociate, leading to the falloff in the caging fraction in the larger clusters.

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Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

“…

Experiments on the photodissociation of ICl -within size-selected CO 2 clusters [Nadal, M. E.;Kleiber, P. D.; Lineberger, W. C. J. Chem. Phys.

…”

mentioning

confidence: 99%

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Simulations of ICl⁻(CO₂)_nPhotodissociation: Effects of Structure, Excited State Charge Flow, and Solvent Dynamics

Faeder

Parson

2009

J. Phys. Chem. A

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“…44 The electron transfer rate in polar solvents has been recently formulated in terms of the fluctuation of local electrostatic potential produced by solvent molecules. 7 According to the model the ET rate constant kET is expressed as: kET = -~J2(p(eAV# ) (1) where q) is a distribution function of the electrostatic potential energy difference eAV between donor and acceptor sites, and J stands for the transfer integral. The specific value o[ the potential difference in Eq.…”

Section: Introduction***mentioning

confidence: 99%

Charge separation reaction in clusters of polar molecules: MD simulations

Hilczer¹,

Kato

Tachiya

1998

J Radioanal Nucl Chem

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Rate constaaat of intermolecular electron transfer (ET) in a photoexcited dono~acceptor model system solvated by a cluster of polar molecules has been expressed in terms of the statistical distribution of the electrostatic potential energy difference between the reacting sites. This distribution has been calculated for a particular case of acetonitrile clusters at ~-120 K by MD computer simulation. The MD values of the cluster reorganization energy and the ET rate constaaat have been compared with the corresponding MD results for the dono~acceptor pair solvated in bulk acetonitrile and with theoretical predictions based on the continuum model.

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Laser photo-induced dissociation using tandem time-of-flight mass spectrometry

Quiniou

Yates

Langridge‐Smith

2000

Rapid Commun. Mass Spectrom.

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A novel tandem time-of-flight (TOF) mass spectrometer has been developed for studying the photo-induced dissociation of large molecules and elemental clusters. It consists of a linear first stage TOF analyser for primary mass separation and precursor ion selection, and a second orthogonal reflecting field TOF analyser for product ion analysis. The instrument is equipped with a large volume throughput molecular beam source chamber allowing the production of jet-cooled molecules and molecular clusters, as well as elemental clusters, using either a pulsed laser vaporisation source (LVS) or a pulsed are cluster ion source (PACIS). A second differentially pumped chamber can be used with effusive sources, or for infrared laser desorption of large molecules, followed by laser ionisation. These primary ions can then be irradiated with a second, high energy laser to induce photodissociation. Detailed information about the fragmentation mechanisms can be deduced from the product ion mass spectra. Preliminary results on the photo-induced dissociation (PID) of the molecule ion of aniline at 266 nm are presented. In this case the molecule ions were generated via two-photon laser ionisation at 266 nm using an effusive source. Results for the collision-induced dissociation (CID) of the aniline molecule ion, using a commercial mass spectrometer equipped with an atmospheric pressure electrospray ionisation interface, are also presented. Copyright 2000 John Wiley & Sons, Ltd.

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Photofragmentation of mass-selected ICl−(CO2)n cluster ions: Solvation effects on the structure and dynamics of the ionic chromophore

Abstract: A 193 nm laser photofragmentation timeofflight mass spectrometric study of CS2 and CS2 clusters

Cited by 68 publications

References 51 publications

Simulations of ICl⁻(CO₂)_nPhotodissociation: Effects of Structure, Excited State Charge Flow, and Solvent Dynamics

Simulations of ICl⁻(CO₂)_nPhotodissociation: Effects of Structure, Excited State Charge Flow, and Solvent Dynamics

Charge separation reaction in clusters of polar molecules: MD simulations

Laser photo-induced dissociation using tandem time-of-flight mass spectrometry

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Photofragmentation of mass-selected ICl−(CO2)n cluster ions: Solvation effects on the structure and dynamics of the ionic chromophore

Abstract: A 193 nm laser photofragmentation timeofflight mass spectrometric study of CS2 and CS2 clusters

Cited by 68 publications

References 51 publications

Simulations of ICl−(CO2)nPhotodissociation: Effects of Structure, Excited State Charge Flow, and Solvent Dynamics

Simulations of ICl−(CO2)nPhotodissociation: Effects of Structure, Excited State Charge Flow, and Solvent Dynamics

Charge separation reaction in clusters of polar molecules: MD simulations

Laser photo-induced dissociation using tandem time-of-flight mass spectrometry

Contact Info

Product

Resources

About

Simulations of ICl⁻(CO₂)_nPhotodissociation: Effects of Structure, Excited State Charge Flow, and Solvent Dynamics

Simulations of ICl⁻(CO₂)_nPhotodissociation: Effects of Structure, Excited State Charge Flow, and Solvent Dynamics