Femtosecond probing of persistent wave packet motion in dissociative reactions: up to 40 ps

Cong, Peijun; Mokhtari, Arash; Zewail, Ahmed H.

doi:10.1016/0009-2614(90)87281-u

Cited by 88 publications

(64 citation statements)

References 22 publications

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“…We exemplify our results with numerical simulations of the predissociation dynamics of NaI. This reaction is a prototype and has already been studied extensively both experimentally [14][15][16][17][18] and theoretically, using semiclassic and quantal calculations. [19][20][21][22][23][24] This paper is organized in the following way: In Sec.…”

Section: Introductionmentioning

confidence: 72%

“…The decay of the peak areas has also been studied experimentally. 17 From the experimental signal, it was indeed concluded that the decay of the peak areas correspond to the rise of the product signal. 17 Here, the areas decayed by 6 ps, which was found to be similar to the fast rise time of free Na ͑for a 310 nm pump͒.…”

Section: Application To Femtosecond Dynamics Of Naimentioning

confidence: 94%

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On the role of coherence in the transition from kinetics to dynamics: Theory and application to femtosecond unimolecular reactions

Møller

Henriksen

Zewail

2000

The Journal of Chemical Physics

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A theory for nonisothermal unimolecular reaction rates J. Chem. Phys. 107, 3542 (1997) We consider the relation between observed pump-probe signals in the femtosecond regime and the kinetics of unimolecular reactions, that is, the exponential decay of reactants and the exponential rise of the product population, respectively. It is shown that the signals cannot be fully accounted for within standard approaches of unimolecular decay, conventionally used in the past, since interference effects between the quasi-bound vibrational states within the bandwidth of the pump laser cannot be neglected. When these effects are included, all features of the signals can be accounted for. We apply this theoretical treatment of coherent interference to examine the dynamics and kinetics of the quasi-bound transition configurations, and relate them to the decay rates of individual quasi-bound resonance states. The signals show multi-exponential behavior, reflecting the different decay rates of the resonance states, with an average rate constant ͑within the bandwidth of the pump laser͒ which can be extracted directly from the signals. The persistence of coherence is evident in the observed signals. The predissociation of NaI is used as a prototype for numerical illustration.

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Section: Introductionmentioning

confidence: 72%

Section: Application To Femtosecond Dynamics Of Naimentioning

confidence: 94%

On the role of coherence in the transition from kinetics to dynamics: Theory and application to femtosecond unimolecular reactions

Møller

Henriksen

Zewail

2000

The Journal of Chemical Physics

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“…10, monitoring the coherence in the nonreactive coordinate, bear a close resemblance to the transients observed in another of the early femtosecond experiments, namely, the study of the electronic pre-dissociation of NaI [39][40][41][42]. The auto-correlation function measures the fraction of molecules in the initial nuclear configuration as a function of time, just like the transient signal in the experiment, if the probe laser is tuned accordingly [24].…”

Section: Comparison With Experimental Observationsmentioning

confidence: 99%

“…The auto-correlation function measures the fraction of molecules in the initial nuclear configuration as a function of time, just like the transient signal in the experiment, if the probe laser is tuned accordingly [24]. The difference here is that the depletion of the signal in the NaI experiments (which involve a one-dimensional PES) is due to dissociation (as well as wave-packet spreading [24] [42]), whereas the depletion in Fig. 10 is due to energy transfer.…”

Section: Comparison With Experimental Observationsmentioning

confidence: 99%

Femtosecond Activation of Reactions: The Concepts of Nonergodic Behavior and Reduced‐Space Dynamics

Møller

Zewail

2001

Essays in Contemporary Chemistry

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“…Due to this feature, there are two possibilities for the fate of alkali halide molecules excited to the covalent state: the wave packet is trapped in the adiabatic PEC and exhibits an oscillation, or it goes on the diabatic PEC and leads to molecular dissociation. It is well known that Zewail and co-workers [1][2][3][4][5] succeeded in observing the real-time wave packet oscillation and decay in the NaI photodissociation using the femtosecond pump-probe technique.…”

Section: Introductionmentioning

confidence: 98%

Ab initio study on the ground and low-lying excited states of cesium iodide (CsI)

Kurosaki

Matsuoka

Yokoyama

et al. 2008

The Journal of Chemical Physics

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Potential energy curves (PECs) for the ground and low-lying excited states of the cesium iodide (CsI) molecule have been calculated using the internally contracted multireference configuration interaction calculation with single and double excitation method with the relativistic pseudopotentials. PECs for seven Lambda-S states, X 1Sigma+, 2 1Sigma+, 3Sigma+, 1Pi, and 3Pi are first calculated and then those for 13 Omega states are obtained by diagonalizing the matrix of the electronic Hamiltonian H(el) plus the effective one-electron spin-orbit (SO) Hamiltonian H(SO). Spectroscopic constants for the calculated ground X 0+-state PEC with the Davidson correction are found to agree well with the experiment. Transition dipole moments (TDMs) between X 0 and the other Omega states are also obtained and the TDM between X 0+ and A 0+ is predicted to be the largest and that between X 0+ and B 0+ is the second largest around the equilibrium internuclear distance. The TDMs between X 0+ and the Omega=1 states are estimated to be nonzero, but they are notably small as compared with those between the 0+ states. Finally, vibrational levels of the X 0+ PEC for the two isotopic analogs, (133)CsI and (135)CsI, are numerically obtained to investigate the isotope effect on the vibrational-level shift. It has been found that the maximized available isotope shift is approximately 30 cm(-1) around nu=136.

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Femtosecond probing of persistent wave packet motion in dissociative reactions: up to 40 ps

Cited by 88 publications

References 22 publications

On the role of coherence in the transition from kinetics to dynamics: Theory and application to femtosecond unimolecular reactions

On the role of coherence in the transition from kinetics to dynamics: Theory and application to femtosecond unimolecular reactions

Femtosecond Activation of Reactions: The Concepts of Nonergodic Behavior and Reduced‐Space Dynamics

Ab initio study on the ground and low-lying excited states of cesium iodide (CsI)

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