Photodissociation and recombination dynamics of I2 in DDR (decadodecasil 3R): Dependence on the geometry of the host matrix monitored by femtosecond time-resolved pump–probe experiments

Flachenecker, G.; Ermoshin, V. A.; Engel, Volker; Neder, Reinhard B.; Wirnsberger, Gernot; Materny, Arnulf

doi:10.1039/b210290k

Cited by 12 publications

(22 citation statements)

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“…The porous crystallites form a channel system, where the iodine guest molecules are embedded. In contrast to the iodine-DDR system investigated earlier, 22 where the iodine molecules are separated from each other in cages, in TON channels the neighboring molecules are allowed to interact with each other. The separated channels which lie parallel to each other have diameters of only Ϸ5 Å for TON 40 ͑Fig.…”

Section: A the Dynamics Of Iodine In Tonmentioning

confidence: 90%

Section: Theorymentioning

confidence: 99%

“…22 We do not repeat a detailed description of this model in this paper and, therefore, refer to the publication of the DDR data. 22,43 For the calculation of the transient absorption signal, reflecting the dynamics along the involved potential curves, about seven valence and seven ion-pair states have to be included. These states are partly not well known since the interaction of iodine with the host system results in a considerable shift of their potential energy ͑this is especially true for the ion-pair states͒.…”

Section: Theorymentioning

confidence: 99%

“…This points to considerably more shifted potential energies for the iodine-TON system compared to the iodine-DDR arrangement. 22 The reason for this is the reduced mobility of the iodine molecules in the narrow channels. Furthermore, the iodineiodine interaction might play a role.…”

Section: Potential Energy Shift Of Iodine In Tonmentioning

confidence: 99%

“…6,7 An important test molecule for the investigation of caging and recombination processes was iodine. Recently, reaction pathways of iodine in different solvent/matrix systems [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] have been studied experimentally. A review of some publications is given in Ref.…”

Section: Introductionmentioning

confidence: 99%

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The elementary steps of the photodissociation and recombination reactions of iodine molecules enclosed in cages and channels of zeolite crystals: A femtosecond time-resolved study of the geometry effect

Flachenecker

Materny

2004

The Journal of Chemical Physics

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We present femtosecond time-resolved pump-probe experiments on iodine molecules enclosed into well-defined cages and channels of different crystalline SiO2 modifications of zeolites. The new experimental results obtained from iodine in TON (Silica-ZSM-22), FER (Silica-Ferrierit), and MFI (Silicalit-1) porosils are compared with data published earlier on the iodine/DDR (Decadodecasil 3R) porosil system [Flachenecker et al., Phys. Chem. Chem. Phys. 5, 865 (2003)]. A summary of all findings is given. The processes analyzed by means of the ultrafast spectroscopy are the vibrational relaxation as well as the dissociation and recombination reactions, which are caused by the interaction of the photo-excited iodine molecules with the cavity walls of the porosils. A clear dependence of the observed dynamics on the geometry of the surrounding lattice structure can be seen. These measurements are supported by temperature-dependent experiments. Making use of a theoretical model which is based on the classical Langevin equation, an analysis of the geometry-reaction relation is performed. The Brownian dynamics simulations show that in contrast to the vibrational relaxation the predissociation dynamics are independent of the frequency of collisions with the surroundings. From the results obtained in the different surroundings, we conclude that mainly local fields are responsible for the crossing from the bound B state to the repulsive a/a' states of the iodine molecules.

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Section: A the Dynamics Of Iodine In Tonmentioning

confidence: 90%

Section: Theorymentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Section: Potential Energy Shift Of Iodine In Tonmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The elementary steps of the photodissociation and recombination reactions of iodine molecules enclosed in cages and channels of zeolite crystals: A femtosecond time-resolved study of the geometry effect

Flachenecker

Materny

2004

The Journal of Chemical Physics

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Intermolecular Electronic Excitation Transfer in a Confined Space: A First‐Principles Study

et al. 2005

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The process of intermolecular electronic excitation transfer (EET) in a monodimensional supramolecular arrangement of molecules in confined space has been modelled and investigated by means of first-principles molecular dynamics simulations. The chosen model system consists of a wire of chlorine molecules hosted in the noncrossing channels of the zeolite bikitaite. The time evolution of the system in its first excited singlet state has been described by the restricted open shell Kohn-Sham formalism. Simulation results have highlighted that excitation, initially localized on a guest molecule, is transferred to an adjacent moiety in the molecular wire on the picosecond scale via a collision-induced Dexter-type short range EET. Analysis of the modifications of the electronic structure of the system brought about by EET has given insight into the microscopic details of the process.

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Supramolecular Organization in Confined Nanospaces

Tabacchi

2018

ChemPhysChem

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Empty spaces are abhorred by nature, which immediately rushes in to fill the void. Humans have learnt pretty well how to make ordered empty nanocontainers, and to get useful products out of them. When such an order is imparted to molecules, new properties may appear, often yielding advanced applications. This review illustrates how the organized void space inherently present in various materials: zeolites, clathrates, mesoporous silica/organosilica, and metal organic frameworks (MOF), for example, can be exploited to create confined, organized, and self-assembled supramolecular structures of low dimensionality. Features of the confining matrices relevant to organization are presented with special focus on molecular-level aspects. Selected examples of confined supramolecular assemblies - from small molecules to quantum dots or luminescent species - are aimed to show the complexity and potential of this approach. Natural confinement (minerals) and hyperconfinement (high pressure) provide further opportunities to understand and master the atomistic-level interactions governing supramolecular organization under nanospace restrictions.

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Photodissociation and recombination dynamics of I2 in DDR (decadodecasil 3R): Dependence on the geometry of the host matrix monitored by femtosecond time-resolved pump–probe experiments

Cited by 12 publications

References 50 publications

The elementary steps of the photodissociation and recombination reactions of iodine molecules enclosed in cages and channels of zeolite crystals: A femtosecond time-resolved study of the geometry effect

The elementary steps of the photodissociation and recombination reactions of iodine molecules enclosed in cages and channels of zeolite crystals: A femtosecond time-resolved study of the geometry effect

Intermolecular Electronic Excitation Transfer in a Confined Space: A First‐Principles Study

Supramolecular Organization in Confined Nanospaces

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