Nonadiabatic molecular dynamics simulations of the photofragmentation and geminate recombination dynamics in size-selected I2−⋅Arn cluster ions

Batista, Víctor S.; Coker, David F.

doi:10.1063/1.473732

Cited by 81 publications

(36 citation statements)

References 51 publications

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“…They not only demonstrate the importance of considering the possibility of nonadiabaticity at the transition state of any chemical reaction with a barrier along the reaction coordinate, they also begin to identify what classes of chemical reactions are most susceptible to these effects. Progress in many groups continues on not only the gas phase front reviewed here, but also on electronically nonadiabatic processes in condensed phases (132)(133)(134)(135)(136)(137)(138)(139). It is the hope of this author that further work in experiment and theory will develop both our ability to achieve an exact quantum prediction for electronically nonadiabatic dynamics and, perhaps more importantly, our intuition for what systems should evidence significant alterations in reaction rates and product branching resulting from a breakdown in the Born-Oppenheimer approximation.…”

Section: Discussionmentioning

confidence: 99%

Chemical Reaction Dynamics Beyond the Born-Oppenheimer Approximation

Butler

1998

Annu. Rev. Phys. Chem.

233

172

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To predict the branching between energetically allowed product channels, chemists often rely on statistical transition state theories or exact quantum scattering calculations on a single adiabatic potential energy surface. The potential energy surface gives the energetic barriers to each chemical reaction and allows prediction of the reaction rates. Yet, chemical reactions evolve on a single potential energy surface only if, in simple terms, the electronic wavefunction can evolve from the reactant electronic configuration to the product electronic configuration on a time scale that is fast compared to the nuclear dynamics through the transition state. The experiments reviewed here investigate how the breakdown of the BornOppenheimer approximation at a barrier along an adiabatic reaction coordinate can alter the dynamics of and the expected branching between molecular dissociation pathways. The work reviewed focuses on three questions that have come to the forefront with recent theory and experiments: Which classes of chemical reactions evidence dramatic nonadiabatic behavior that influences the branching between energetically allowed reaction pathways? How do the intramolecular distance and orientation between the electronic orbitals involved influence the nonadiabaticity in the reaction? How can the detailed nuclear dynamics mediate the effective nonadiabatic coupling encountered in a chemical reaction?

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Section: Discussionmentioning

confidence: 99%

Chemical Reaction Dynamics Beyond the Born-Oppenheimer Approximation

Butler

1998

Annu. Rev. Phys. Chem.

233

172

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“…1, 2 For ionic molecules, the possibility of mass selection by relatively simple electrostatic devices allows experimentalists to investigate this phenomenon for a perfectly controlled number of solvent atoms. [10][11][12] This process is quite general for charged molecules, and we have recently shown that it takes place for Na + 2 cation embedded in the first solvation shell of Ar clusters. [5][6][7][8][9] For the prototypical case of I − 2 dimer embedded in such clusters, it has been shown that photoexcitation leads to geminate recombination of the anion in its ground state for clusters made of a few solvent units only.…”

Section: Introductionmentioning

confidence: 95%

Nonadiabatic molecular dynamics of photoexcited ${\rm Li}_2^+{\rm Ne}_n$ Li 2+ Ne n clusters

Zanuttini¹,

Douady²,

Jacquet³

et al. 2011

The Journal of Chemical Physics

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We investigate the relaxation of photoexcited Li(2)(+) chromophores solvated in Ne(n) clusters (n = 2-22) by means of molecular dynamics with surface hopping. The simplicity of the electronic structure of these ideal systems is exploited to design an accurate and computationally efficient model. These systems present two series of conical intersections between the states correlated with the Li+Li(2s) and Li+Li(2p) dissociation limits of the Li(2)(+) molecule. Frank-Condon transition from the ground state to one of the three lowest excited states, hereafter indexed by ascending energy from 1 to 3, quickly drives the system toward the first series of conical intersections, which have a tremendous influence on the issue of the dynamics. The states 1 and 2, which originate in the Frank-Condon area from the degenerated nondissociative 1(2)Π(u) states of the bare Li(2)(+) molecule, relax mainly to Li+Li(2s) with a complete atomization of the clusters in the whole range of size n investigated here. The third state, which originates in the Frank-Condon area from the dissociative 1(2)Σ(u)(+) state of the bare Li(2)(+) molecule, exhibits a richer relaxation dynamics. Contrary to intuition, excitation into state 3 leads to less molecular dissociation, though the amount of energy deposited in the cluster by the excitation process is larger than for excitation into state 1 and 2. This extra amount of energy allows the system to reach the second series of conical intersections so that approximately 20% of the clusters are stabilized in the 2(2)Σ(g)(+) state potential well for cluster sizes n larger than 6.

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“…[42] Photodissociation, geminate recombination, and relaxation dynamics were investigated in size-selected I 2 C À ·n Ar clusters by using a coupled quantum-classical MD procedure and a model Hamiltonian. [43] However, till now only one theoretical study on hydrated I 2 C À cluster has been reported in the literature. [32] In this study, stability and IR spectra of I 2 C À ·n H 2 O clusters (n 10) were studied by DFT methods.…”

Section: Introductionmentioning

confidence: 98%

Global Minimum‐Energy Structure and Spectroscopic Properties of I₂^.−⋅n H₂O Clusters: A Monte Carlo Simulated Annealing Study

2010

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The vibrational (IR and Raman) and photoelectron spectral properties of hydrated iodine-dimer radical-anion clusters, I(2)(*-) x n H(2)O (n=1-10), are presented. Several initial guess structures are considered for each size of cluster to locate the global minimum-energy structure by applying a Monte Carlo simulated annealing procedure including spin-orbit interaction. In the Raman spectrum, hydration reduces the intensity of the I-I stretching band but enhances the intensity of the O-H stretching band of water. Raman spectra of more highly hydrated clusters appear to be simpler than the corresponding IR spectra. Vibrational bands due to simultaneous stretching vibrations of O-H bonds in a cyclic water network are observed for I(2)(*-) x n H(2)O clusters with n > or = 3. The vertical detachment energy (VDE) profile shows stepwise saturation that indicates closing of the geometrical shell in the hydrated clusters on addition of every four water molecules. The calculated VDE of finite-size small hydrated clusters is extrapolated to evaluate the bulk VDE value of I(2)(*-) in aqueous solution as 7.6 eV at the CCSD(T) level of theory. Structure and spectroscopic properties of these hydrated clusters are compared with those of hydrated clusters of Cl(2)(*-) and Br(2)(*-).

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Nonadiabatic molecular dynamics simulations of the photofragmentation and geminate recombination dynamics in size-selected I2−⋅Arn cluster ions

Cited by 81 publications

References 51 publications

Chemical Reaction Dynamics Beyond the Born-Oppenheimer Approximation

Chemical Reaction Dynamics Beyond the Born-Oppenheimer Approximation

Nonadiabatic molecular dynamics of photoexcited ${\rm Li}_2^+{\rm Ne}_n$ Li 2+ Ne n clusters

Global Minimum‐Energy Structure and Spectroscopic Properties of I₂^.−⋅n H₂O Clusters: A Monte Carlo Simulated Annealing Study

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Nonadiabatic molecular dynamics simulations of the photofragmentation and geminate recombination dynamics in size-selected I2−⋅Arn cluster ions

Cited by 81 publications

References 51 publications

Chemical Reaction Dynamics Beyond the Born-Oppenheimer Approximation

Chemical Reaction Dynamics Beyond the Born-Oppenheimer Approximation

Nonadiabatic molecular dynamics of photoexcited ${\rm Li}_2^+{\rm Ne}_n$ Li 2+ Ne n clusters

Global Minimum‐Energy Structure and Spectroscopic Properties of I2.−⋅n H2O Clusters: A Monte Carlo Simulated Annealing Study

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Global Minimum‐Energy Structure and Spectroscopic Properties of I₂^.−⋅n H₂O Clusters: A Monte Carlo Simulated Annealing Study