Control of non-adiabatic photodissociation of sodium iodide using ultrashort pump and control pulses

Taneichi, Takashi; Kobayashi, Takayoshi; Ohtsuki, Yukiyoshi; Fujimura, Y.

doi:10.1016/0009-2614(94)01220-2

Cited by 25 publications

(9 citation statements)

References 20 publications

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“…Alternatively, optical processes can be calculated using a direct integration of the equations of motion in the presence of the fields. By calculating the relevant wave function 25 or density matrix elements [26][27][28][29][30][31][32][33] it becomes possible to explore optical processes for a system with arbitrary potential surfaces. A difficulty with this approach is the proper treatment of dephasing processes induced by a heat bath.…”

Section: Introductionmentioning

confidence: 99%

Gaussian–Markovian quantum Fokker–Planck approach to nonlinear spectroscopy of a displaced Morse potentials system: Dissociation, predissociation, and optical Stark effects

Tanimura¹,

Maruyama²

1997

The Journal of Chemical Physics

107

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Quantum coherence and its dephasing by coupling to a dissipative environment play an important role in time-resolved nonlinear optical response as well as nonadiabatic transitions in the condensed phase. We have discussed nonlinear optical processes on a multi-state one-dimensional system with Morse potential surfaces in a dissipative environment. This was based on a numerical study using the multi-state quantum Fokker-Planck equation for a colored Gaussian-Markovian noise bath, which was expressed as a hierarchy of kinetic equations. This equation can treat strong system-bath interactions at a low temperature heat bath, where quantum effects play a major role. The approach applies to linear absorption measurements as well as four-wave mixing including pump-probe spectroscopy. Laser induced photodissociation and predissociation have been studied for the potential surfaces of Cs 2. We have calculated nuclear wave packets in Wigner representation and their monitoring by femtosecond pump-probe spectroscopy for various displacements of potentials and heat-bath parameters. Numerical calculations of probe absorption spectra for strong pump pulse are also presented and discussed. The results show dynamical Stark splitting, but, in contrast to the Bloch equations which contain an infinite-temperature dephasing, we find that at finite temperature their peaks have different heights even when the pump pulse is on resonance.

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Section: Introductionmentioning

confidence: 99%

Gaussian–Markovian quantum Fokker–Planck approach to nonlinear spectroscopy of a displaced Morse potentials system: Dissociation, predissociation, and optical Stark effects

Tanimura¹,

Maruyama²

1997

The Journal of Chemical Physics

107

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“…In general, the existence and possible role of quantum coherence in this non-ergodic motion remains a critical question [36][37][38]; quantum coherence requires much more than just ordered classical motion as the phase difference between quantum wavepackets propagating through equilibrium systems in thermal environments must also be maintained, generating quantum entanglement [39]. Not just transition states are now studied by also photochemical species existing down to ultrashort timescales with wide ranging applications in energy harvesting and catalysis, as revealed, e.g., by the works of Kobayashi [40][41][42][43][44][45][46][47][48][49][50].…”

Section: Introductionmentioning

confidence: 99%

Relating transition-state spectroscopy to standard chemical spectroscopic processes

Reimers

Hush

2017

Chemical Physics Letters

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Transition-state spectra are mapped out using generalized adiabatic electron-transfer theory. This simple model depicts diverse chemical properties, from aromaticity, through bound reactions such as isomerizations and atom-transfer processes with classic transition states, to processes often described as being "non-adiabatic", to those in the "inverted" region that become slower as they are made more exothermic. Predictably, the Born-Oppenheimer approximation is found inadequate for modelling transition-state spectra in the weak-coupling limit. In this limit, the adiabatic Born-Huang approximation is found to perform much better than non-adiabatic surfacehopping approaches. Transition-state spectroscopy is shown to involve significant quantum entanglement between electronic and nuclear motion. Highlights-transition-state spectra are calculated over a wide parameter region-spectral and temporal responses may be simple or quite complex-surface hopping methods fail to describe spectra usually classified as "non-adiabatic"-transition-state spectroscopy embodies quantum entanglement

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“…The interference quenches the fluorescence [16,[24][25][26][27][28][29]. The geometric phase is sensitive to the wave packet's angular momentum [35,36], which can be controlled by tuning the spectral phase of the laser pulse [37]. Theoretically, angular momentum is added to a wave packet by multiplying it by il e  , where  is the phase, and l is the angular momentum [36].…”

Section: Introductionmentioning

confidence: 99%

Molecular level crossing and the geometric phase effect from the optical Hanle perspective

Glenn

Dantus²

2016

Phys. Rev. A

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Level-crossing spectroscopy involves lifting the degeneracy of an excited state and using the interference of two nearly degenerate levels to measure the excited state lifetime. Here we use the idea of interference between different pathways to study the momentum-dependent wave packet lifetime due an excited state level-crossing (conical intersection) in a molecule. Changes in population from the wave packet propagation are reflected in the detected fluorescence. We use a chirped pulse to control the wave packet momentum. Changing the chirp rate affects the transition to the lower state through the conical intersection. It also affects the interference of different pathways in the upper electronic state, due to the geometric phase acquired. Increasing the chirp rate decreases the coherence of the wave packet in the upper electronic state. This suggests that there is a finite momentum dependent lifetime of the wave packet through the level-crossing as function of chirp. We dub this lifetime the wave packet momentum lifetime. : 33.15.Hp, 32.50.+d, 33.80.Be, 78.20.Bh, 42.65.Re ( b ). When both levels are nearly degenerate and excited simultaneously, the fluorescence is proportional to   2 ab AA  . Resonance occurs when the magnetic field is zero and increasing the magnetic field strength partially destroys the coherence. Thus, the absolute radiative lifetime can be measured by detecting the fluorescence as a function magnetic field strength, without any knowledge of the density of the emitters [13]. Electronic level-crossings (conical intersections) occur in nearly all molecules and are responsible for many excitedstate chemical processes [2][3][4][14][15][16]. The isomerization PACS

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Control of non-adiabatic photodissociation of sodium iodide using ultrashort pump and control pulses

Cited by 25 publications

References 20 publications

Gaussian–Markovian quantum Fokker–Planck approach to nonlinear spectroscopy of a displaced Morse potentials system: Dissociation, predissociation, and optical Stark effects

Gaussian–Markovian quantum Fokker–Planck approach to nonlinear spectroscopy of a displaced Morse potentials system: Dissociation, predissociation, and optical Stark effects

Relating transition-state spectroscopy to standard chemical spectroscopic processes

Molecular level crossing and the geometric phase effect from the optical Hanle perspective

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