Time-resolved photoelectron spectroscopy of wavepackets through a conical intersection in NO2

Arasaki, Yasuki; Takatsuka, Kazuo; Wang, Kwanghsi; McKoy, Vincent

doi:10.1063/1.3369647

Cited by 105 publications

(118 citation statements)

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“…For later times (16 and 20 fs), a strong 2S component signal develops as the wavepacket on diabatic state 2 reaches the turning point at small angles. These overall changes in the photoelectron angular distributions were noted in the previous paper 34 without a control pulse.…”

Section: Time-resolved Photoelectron Angular Distributions Reflectingsupporting

confidence: 75%

“…6 of the previous paper. 34 Fig . 6 shows that the overall time evolution of the photoelectron images in Fig.…”

Section: Time-resolved Photoelectron Angular Distributions Reflectingmentioning

confidence: 99%

“…22 We have also previously demonstrated the utility of time-resolved photoelectron spectra, along with the need to incorporate geometry-and energy-dependent photoionization matrix elements in such studies, in a series of papers tracking wavepacket dynamics in different scenarios: vibrational motion across a one-dimensional double-well potential in an excited state of Na 2 , [23][24][25][26][27] wavepacket bifurcation at an avoided crossing in NaI, 28,29 and proton transfer in the ground state of chloromalonaldehyde. [30][31][32] Anticipating that advances in ultrashort pulse shaping technology may also well enable the observation of wavepacket dynamics through a CI on the actual time scale of the nonadiabatic transition, we recently studied the photoelectron energy and angular distributions expected in and around the CI between the lowest 2 A 0 states of the NO 2 molecule 33,34 and showed that the photoelectron signals, particularly the angular distributions, provide a valuable window on wavepacket dynamics there. Exploiting the results of these two studies, 15,33,34 here we show with full quantum mechanical calculations that such optical control of a conical intersection can actually be monitored in real time with femtosecond angle-and energy-resolved photoelectron spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

“…[30][31][32] Anticipating that advances in ultrashort pulse shaping technology may also well enable the observation of wavepacket dynamics through a CI on the actual time scale of the nonadiabatic transition, we recently studied the photoelectron energy and angular distributions expected in and around the CI between the lowest 2 A 0 states of the NO 2 molecule 33,34 and showed that the photoelectron signals, particularly the angular distributions, provide a valuable window on wavepacket dynamics there. Exploiting the results of these two studies, 15,33,34 here we show with full quantum mechanical calculations that such optical control of a conical intersection can actually be monitored in real time with femtosecond angle-and energy-resolved photoelectron spectroscopy. This suggests that one can optimally control the above gating process through the conical intersection by a feedback loop based on varying the control parameters and monitoring the photoelectron velocity map images.…”

Section: Introductionmentioning

confidence: 99%

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Monitoring the effect of a control pulse on a conical intersection by time-resolved photoelectron spectroscopy

Arasaki

Wang

McKoy

et al. 2011

Phys. Chem. Chem. Phys.

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We have previously shown how femtosecond angle-and energy-resolved photoelectron spectroscopy can be used to monitor quantum wavepacket bifurcation at an avoided crossing or conical intersection and also how a symmetry-allowed conical intersection can be effectively morphed into an avoided crossing by photo-induced symmetry breaking. The latter result suggests that varying the parameters of a laser to modify a conical intersection might control the rate of passage of wavepackets through such regions, providing a gating process for different chemical products. In this paper, we show with full quantum mechanical calculations that such optical control of conical intersections can actually be monitored in real time with femtosecond angle-and energy-resolved photoelectron spectroscopy. In turn, this suggests that one can optimally control the gating process at a conical intersection by monitoring the photoelectron velocity map images, which should provide far more efficient and rapid optimal control than measuring the ratio of products. To demonstrate the sensitivity of time-resolved photoelectron spectra for detecting the consequences of such optical control, as well as for monitoring how the wavepacket bifurcation is affected by the control, we report results for quantum wavepackets going through the region of the symmetry-allowed conical intersection between the first two 2 A 0 states of NO 2 that is transformed to an avoided crossing. Geometry-and energy-dependent photoionization matrix elements are explicitly incorporated in these studies. Time-resolved photoelectron angular distributions and photoelectron images are seen to systematically reflect the effects of the control pulse.

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Section: Time-resolved Photoelectron Angular Distributions Reflectingsupporting

confidence: 75%

“…6 of the previous paper. 34 Fig . 6 shows that the overall time evolution of the photoelectron images in Fig.…”

Section: Time-resolved Photoelectron Angular Distributions Reflectingmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Monitoring the effect of a control pulse on a conical intersection by time-resolved photoelectron spectroscopy

Arasaki

Wang

McKoy

et al. 2011

Phys. Chem. Chem. Phys.

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“…Angle-resolved measurements in the molecular frame-TRMFPADs-provide the most detailed information on e and, hence, the evolving valence-electronic structure of i (t ). Theoretical studies previously suggested the possibility, in nonadiabatic wavepacket dynamics, that angle-resolved measurements will be useful 28,29 . So far, however, experimental studies have been restricted to corroborating excited-state dynamics inferred from TRPES studies and ab initio dynamics calculations 14,15 .…”

mentioning

confidence: 99%

Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

et al. 2011

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Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems [1][2][3][4][5][6] . By contrast, time-resolved structural-dynamics methods such as electron 7-10 or X-ray diffraction 11 and X-ray absorption 12 yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy 13-15 and high-harmonic generation 16,17 : in both cases, this sensitivity derives from the ionization-matrix element 18,19 . Here we demonstrate a time-resolved molecularframe photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during the non-adiabatic photodissociation of carbon disulphide demonstrate how the purely electronic rearrangements of the valence electrons can be projected from inherently coupled electronic-vibrational dynamics. Combined with ongoing efforts in molecular frame alignment 20 and orientation 21,22 , TRMFPADs offer the promise of directly imaging valenceelectron dynamics during molecular processes without involving the use of strong, highly perturbing laser fields 23 . Figure 1 provides a conceptual overview of our method. Carbon disulphide, CS 2 , is a molecule that exhibits all the features generic to polyatomic dynamics: vibrational mode coupling, conical intersections, spin conversion and photodissociation. As such, its non-adiabatic photodissociation reaction CS 2 (X ) Fig. 1, provides an excellent test. In this work we combine experimental measurements with theory to demonstrate how the TRMFPAD images the evolution of the valence-electronic structure of an excited-state wavepacket during the complex, coupled electronnuclear processes inherent to chemical reactions. TRMFPADs probe both nuclear and electronic degrees of freedom through the photoionization matrix elements, d(t ) = + ; e |μ ·E| i (t ) . These matrix elements describe how the initial wavepacket, and its subsequent evolution in time ( i (t )), is projected onto the ionization continuum, consisting of the cation ( + ) and photoelectron ( e ) states, through dipole coupling (μ) with the laser field (E; refs 18,24). In the case of polyatomic molecules, i (t ) and + are composed of coupled electronic and vibrational components (see Supplementary Information). The significance of the TRMFPAD can be understood by considering the intimate relationship between e and the electronic part of i (t ). For example, under the well-known Born (plane-wave) approximation, 1 Steacie Institute for Molecular Sciences, National Research Council, 100 Sussex Drive, Ottawa, Ontario K1A 0R6, Canada, 2 Department of Chemistry, University of Copenhagen, Copenhagen DK-2100, Denmark, 3 Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada. *e-mail: alb...

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Pulse‐Train Photoelectron Spectroscopy of Electronic and Nuclear Dynamics in Molecules

Arasaki

Takatsuka

2013

ChemPhysChem

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We theoretically study the application of a femtosecond pulse train to simultaneously probe the electronic excitation dynamics and nuclear vibrational motion in the excited-state LiH molecule by means of time-resolved photoelectron spectroscopy. The step-like population transfers caused by continual interaction with a sequence of pulses and refractory periods are shown to give rise to time evolution of the photoelectron kinetic energy distribution as the history of molecular electronic and vibrational states. Such a signal should lead to a novel and direct way to investigate electronic and nuclear simultaneous dynamics involving multiple excited states.

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Time-resolved photoelectron spectroscopy of wavepackets through a conical intersection in NO2

Cited by 105 publications

References 50 publications

Monitoring the effect of a control pulse on a conical intersection by time-resolved photoelectron spectroscopy

Monitoring the effect of a control pulse on a conical intersection by time-resolved photoelectron spectroscopy

Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

Pulse‐Train Photoelectron Spectroscopy of Electronic and Nuclear Dynamics in Molecules

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