Structural dynamics effects on the ultrafast chemical bond cleavage of a photodissociation reaction

Corrales, María Elena; Loriot, V.; Balerdi, Garikoitz; González‐Vázquez, Jesús; Nalda, R. de; Bañares, Luis; Zewail, Ahmed H.

doi:10.1039/c3cp54677b

Cited by 51 publications

(76 citation statements)

References 25 publications

(31 reference statements)

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“…[178] Using MCSCF or MRCI, already a number of ISC dynamics simulations have been reported using SHARC. [108,[114][115][116]188,189] The progress of general ab initio molecular dynamics schemes like SHARC strongly depends on the development of electronic structure methods that can go beyond MCSCF, which is one of the most popular methods for on-the-fly excited-state dynamics. A obvious step further is completeactive-space perturbation theory (e.g., CASPT2 [190] ), which offers very good accuracy (oftentimes better than MRCI) and performance (usually much faster than MRCI).…”

Section: Discussionmentioning

confidence: 99%

A general method to describe intersystem crossing dynamics in trajectory surface hopping

Mai

Marquetand

González

2015

Int J of Quantum Chemistry

264

406

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Intersystem crossing is a radiationless process that can take place in a molecule irradiated by UV‐Vis light, thereby playing an important role in many environmental, biological and technological processes. This paper reviews different methods to describe intersystem crossing dynamics, paying attention to semiclassical trajectory theories, which are especially interesting because they can be applied to large systems with many degrees of freedom. In particular, a general trajectory surface hopping methodology recently developed by the authors, which is able to include nonadiabatic and spin‐orbit couplings in excited‐state dynamics simulations, is explained in detail. This method, termed SHARC, can in principle include any arbitrary coupling, what makes it generally applicable to photophysical and photochemical problems, also those including explicit laser fields. A step‐by‐step derivation of the main equations of motion employed in surface hopping based on the fewest‐switches method of Tully, adapted for the inclusion of spin‐orbit interactions, is provided. Special emphasis is put on describing the different possible choices of the electronic bases in which spin‐orbit can be included in surface hopping, highlighting the advantages and inconsistencies of the different approaches. © 2015 Wiley Periodicals, Inc.

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Section: Discussionmentioning

confidence: 99%

A general method to describe intersystem crossing dynamics in trajectory surface hopping

Mai

Marquetand

González

2015

Int J of Quantum Chemistry

264

406

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“…It is important to note that the multidimensional nature of the fit allows the discrimination of the different contributions to the images, in a manner that a reduced-dimensionality analysis cannot achieve. This method has revealed its value in a number of contributions where the need for discrimination of overlapping contributions in charged particle images was crucial [13][14][15][16][17][18]. The method is analogous to the global 2D fit approach used in Stolow's group [19][20][21][22] but can easily be extended to extra dimensions such as the anisotropy, the temperature, the intensity dependence, measurements in coincidence, etc.…”

Section: Introductionmentioning

confidence: 99%

Multidimensional Analysis of Time-Resolved Charged Particle Imaging Experiments

2018

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Abstract:We present a tutorial to realize a multidimensional fitting procedure capable of extracting all the relevant information contained in a sequence of charged particle images acquired as a function of time in femtosecond pump-probe experiments. The images are reproduced using a 3D fitting method, which provides the velocity (or center-of-mass kinetic energy) and angular distributions contained in the images and their time evolution. A detailed example of the method is shown through the analysis of the time-resolved predissociation dynamics of CH 3 I on the B-band origin (Gitzinger et al., J. Chem. Phys. 2010, 133, 234313). We show that the multidimensional approach is essential for the analysis of complex images that contain several overlapping contributions where reduced dimensionality analyses cannot provide a reliable description of the features present in the image sequence. This methodology can be generalized to many types of multidimensional data analysis.

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“…26 While the latter probe the asymptotic atomic products, the shifts of the emerging XUV transitions represent the relaxation of the valence shell vacancy, which we find to take place during the very first moments of dissociation.…”

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confidence: 99%

“…Our experimental raw data for CH 3 I appear to be consistent with the data of Attar et al While we cannot rule out such distinct transient intermediate resonances in CH 3 I, we believe that our interpretation of the data as a weak energy shift of the valence shell hole is a straightforward alternative that should be considered. The much shorter time scales as compared to complete dissociation 26 suggest that in CH 3 I very little nuclear motion is involved in the relaxation of the valence shell vacancy, attributed to its nature originating from the iodine lone pair. In view of the marked difference observed for iodobenzene, XUV transient absorption is anticipated to be sensitive to the coupled electronic and structural dynamics in molecules.…”

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confidence: 99%

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Electric-field-driven electron-transfer in mixed-valence molecules

Blair

Corcelli

Lent

2016

The Journal of Chemical Physics

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Molecular quantum-dot cellular automata is a computing paradigm in which digital information is encoded by the charge configuration of a mixed-valence molecule. General-purpose computing can be achieved by arranging these compounds on a substrate and exploiting intermolecular Coulombic coupling. The operation of such a device relies on nonequilibrium electron transfer (ET), whereby the time-varying electric field of one molecule induces an ET event in a neighboring molecule. The magnitude of the electric fields can be quite large because of close spatial proximity, and the induced ET rate is a measure of the nonequilibrium response of the molecule. We calculate the electric-field-driven ET rate for a model mixed-valence compound. The mixed-valence molecule is regarded as a two-state electronic system coupled to a molecular vibrational mode, which is, in turn, coupled to a thermal environment. Both the electronic and vibrational degrees-of-freedom are treated quantum mechanically, and the dissipative vibrational-bath interaction is modeled with the Lindblad equation. This approach captures both tunneling and nonadiabatic dynamics. Relationships between microscopic molecular properties and the driven ET rate are explored for two time-dependent applied fields: an abruptly switched field and a linearly ramped field. In both cases, the driven ET rate is only weakly temperature dependent. When the model is applied using parameters appropriate to a specific mixed-valence molecule, diferrocenylacetylene, terahertz-range ET transfer rates are predicted.

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Structural dynamics effects on the ultrafast chemical bond cleavage of a photodissociation reaction

Cited by 51 publications

References 25 publications

A general method to describe intersystem crossing dynamics in trajectory surface hopping

A general method to describe intersystem crossing dynamics in trajectory surface hopping

Multidimensional Analysis of Time-Resolved Charged Particle Imaging Experiments

Electric-field-driven electron-transfer in mixed-valence molecules

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