Quantum ignition of intramolecular rotation by means of IR + UV laser pulses

Fujimura, Y.; González, Leticia; Kröner, Dominik; Manz, J.; Mehdaoui, Imed; Schmidt, Burkhard

doi:10.1016/j.cplett.2004.01.070

Cited by 43 publications

(45 citation statements)

References 30 publications

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“…Keeping the rotation alive requires further input of energy, e.g., by repeating pump-dump UV-laser pulses. 14 The rotor design approach advocated in the present work differs in several respects from the approaches mentioned above. Most importantly, Brownian motion of the heat bath typically has a detrimental effect on the action of the rotors cited above, whereas we aim at the design of "Brownian rotors" for which random interaction with the heat bath is incorporated into the working principle and could even be considered the driving force.…”

Section: Introductionmentioning

confidence: 54%

“…Most importantly, Brownian motion of the heat bath typically has a detrimental effect on the action of the rotors cited above, whereas we aim at the design of "Brownian rotors" for which random interaction with the heat bath is incorporated into the working principle and could even be considered the driving force. In contrast to the rotors by Koumura et al 4,5 and Fujimura et al, 14 we have to design a rotational potential of suitable form only in one electronic state ͑the ground state͒; as will be shown in the main part of this article, this task is already a difficult one. Similar to the rotors mentioned above, we also utilize a switching process, but the switching molecular unit is not directly associated with the rotation axis, again lending more flexibility to the molecular design.…”

Section: Introductionmentioning

confidence: 99%

“…Hoki et al 12,13 and Fujimura et al 14 have presented variations in another basic concept, namely, to "kick-start" a rotation by suitable IR-and UV-laser pulse sequences. First, a spatially compact ground state wavepacket is prepared, which is then pumped to an excited state where the rotation is started ͑or promoted further͒ by the action of a suitable potential gradient.…”

Section: Introductionmentioning

confidence: 99%

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Brownian molecular rotors: Theoretical design principles and predicted realizations

Schönborn

Herges

Hartke

2009

The Journal of Chemical Physics

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Section: Introductionmentioning

confidence: 54%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Brownian molecular rotors: Theoretical design principles and predicted realizations

Schönborn

Herges

Hartke

2009

The Journal of Chemical Physics

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“…In addition, because of intramolecular vibrational redistribution (IVR) in and conical intersections of excited states (or other non-adiabatic couplings) one typically needs to move the population rapidly through the transition state, which favors doing it in the absence of a barrier in the excited state. Using strong fields to drive the electronic absorption leads naturally to study the effect of vibrational motion (or vibrational coherence) to enhance such absorption [59][60][61][62][63][64][65][66][67]. Recent results in two-photon processes (such as a pump-dump mechanism) have shown that the optimization of the initial wave packet is less important when the pulses are time-delayed [68].…”

Section: Introductionmentioning

confidence: 99%

Geometrical Optimization Approach to Isomerization: Models and Limitations

et al. 2017

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We study laser-driven isomerization reactions through an excited electronic state using the recently developed Geometrical Optimization procedure [J. Phys. Chem. Lett. 6, 1724Lett. 6, (2015]. The goal is to analyze whether an initial wave packet in the ground state, with optimized amplitudes and phases, can be used to enhance the yield of the reaction at faster rates, exploring how the geometrical restrictions induced by the symmetry of the system impose limitations in the optimization procedure. As an example we model the isomerization in an oriented 2,2'-dimethyl biphenyl molecule with a simple quartic potential. Using long (picosecond) pulses we find that the isomerization can be achieved driven by a single pulse. The phase of the initial superposition state does not affect the yield. However, using short (femtosecond) pulses, one always needs a pair of pulses to force the reaction. High yields can only be obtained by optimizing both the initial state, and the wave packet prepared in the excited state, implying the well known pump-dump mechanism.

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“…Being able to exert control over intersystem crossing or over any nonradiative decay pathway of molecular excited states potentially has important applications. For example, it could lead to control over photochemical reactions (2), more efficient dyes in fluorescence microscopy (3), driving of molecular motors (4), and other photonic applications. However, mixing between the ''optically bright'' state and the bath of ''optically dark'' states is generally viewed to be statistical, and as such offers no possibility for the design and application of rational coherent control schemes.…”

mentioning

confidence: 99%

Interference in acetylene intersystem crossing acts as the molecular analog of Young's double-slit experiment

Groot

Field

Buma

2009

Proc. Natl. Acad. Sci. U.S.A.

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We report on an experimental approach that reveals crucial details of the composition of singlet-triplet mixed eigenstates in acetylene. Intersystem crossing in this prototypical polyatomic molecule embodies the mixing of the lowest excited singlet state (S1) with 3 triplet states (T1, T2, and T3). Using high-energy (157-nm) photons from an F2 laser to record excited-state photoelectron spectra, we have decomposed the mixed eigenstates into their S1, T3, T2, and T1 constituent parts. One example of the interpretive power that ensues from the selective sensitivity of the experiment to the individual electronic state characters is the discovery and examination of destructive interference between two doorway-mediated intersystem crossing pathways. This observation of an interference effect in nonradiative decay opens up possibilities for rational coherent control over molecular excited state dynamics.Decomposition mixed eigenstates ͉ Nonradiative decay interference ͉ Photoelectron spectroscopy S inglet-triplet intersystem crossing (ISC) is a fundamental nonradiative decay pathway for molecular electronically excited states. At its basis is the spin-orbit interaction that mixes low-lying vibrational levels of a singlet state with isoenergetic highly excited vibrational levels of lower-lying triplet electronic states (1). Being able to exert control over intersystem crossing or over any nonradiative decay pathway of molecular excited states potentially has important applications. For example, it could lead to control over photochemical reactions (2), more efficient dyes in fluorescence microscopy (3), driving of molecular motors (4), and other photonic applications. However, mixing between the ''optically bright'' state and the bath of ''optically dark'' states is generally viewed to be statistical, and as such offers no possibility for the design and application of rational coherent control schemes. Sometimes the interaction between bright and dark states is locally promoted by a ''doorway'' state* (5-8) that facilitates stronger indirect mixing than would occur in the case of direct interaction between bright and dark states. Nevertheless, even for ISC mediated by a doorway state, control schemes cannot go beyond a simple energy and temporal control based on prior knowledge of specific spectroscopic details, such as the choice to excite close to or far from the doorway state.It is only after an appropriate experimental approach has been devised to understand the mechanism of ISC that one may hope to exert full external control over ISC. Typically, studies of intersystem crossing focus on its effects in the time domain, i.e., the evolution of the relevant electronic state populations is followed after excitation of the singlet state. However, with this approach details of interaction mechanisms are very difficult to determine when vibrational levels of more than one triplet electronic state lie below the singlet state. Clearly, determining the composition of the mixed wavefunctions in terms of all of their contribut...

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Quantum ignition of intramolecular rotation by means of IR + UV laser pulses

Cited by 43 publications

References 30 publications

Brownian molecular rotors: Theoretical design principles and predicted realizations

Brownian molecular rotors: Theoretical design principles and predicted realizations

Geometrical Optimization Approach to Isomerization: Models and Limitations

Interference in acetylene intersystem crossing acts as the molecular analog of Young's double-slit experiment

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