The role of phase in molecular Rydberg wave packet dynamics

Smith, R. A. L.; Stavros, Vasilios G.; Verlet, Jan R. R.; Fielding, Helen H.; Townsend, David; Softley, T. P.

doi:10.1063/1.1589473

Cited by 16 publications

(8 citation statements)

References 28 publications

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“…Part of this complexity comes from the many interacting states that lie extremely close in energy. An alternative route to understanding these systems is through the study of their dynamics using time resolved spectroscopy methods [5,6], generally requiring femtosecond to picosecond pulses of laser radiation. Since the maximum photon energy available in a conventional femtosecond laser system is limited to ∼6 eV, excitation of highly excited electronic states requires the use of multiphoton excitation schemes [7,8].…”

Section: Introductionmentioning

confidence: 99%

VUV excitation of a vibrational wavepacket in D₂measured through strong-field dissociative ionization

et al. 2015

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Femtosecond vacuum ultraviolet pulses from a monochromated high harmonic generation source excite vibrational wavepackets in the B 1 g S + state of D 2 . The wavepacket motion is measured through strong field ionization into bound and dissociative ion states yielding D 2 + and D + products. The time dependence of the D 2 + and D + ion signals provides a sensitive fingerprint of the quantum nuclear wavepacket, due to the different ionization rates for the two channels. The experiments are modelled with excitation and ionization processes included explicitly, with the results of the model showing a very good agreement with the experimental observations. The experiment demonstrates the level of detail attainable when studying ultrafast quantum nuclear dynamics using high harmonic sources.

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Section: Introductionmentioning

confidence: 99%

VUV excitation of a vibrational wavepacket in D₂measured through strong-field dissociative ionization

et al. 2015

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“…2(a) shows the experimental recurrence spectrum following excitation of a single wave packet. The first recurrence exhibits the double peak structure that has been observed in previous experiments [15]. The dip corresponds to destructive interference between the two wave packets when they return to the core with an accumulated phase difference of , and is observed at time t ave .…”

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confidence: 68%

“…When both wave packets return to the core and overlap spatially (i.e., t t a cl t b cl , which is true for 2 2 a E rot 1) they will interfere with one another, and Eq. (1) can be rearranged to give the stroboscopic periods T s T rot k for 2 k [15]. These interference effects have been observed in time-resolved spectra of molecular Rydberg wave packets in NO, manifesting themselves as plateaus in plots of the observed recurrence time as a function of the average principal quantum number in the superposition.…”

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confidence: 99%

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Optical Control of the Rotational Angular Momentum of a Molecular Rydberg Wave Packet

et al. 2003

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An intuitive scheme for controlling the rotational quantum state of a Rydberg molecule is demonstrated experimentally. We determine the accumulated phase difference between the various components of a molecular electron wave packet, and then employ a sequence of phase-locked optical pulses to selectively enhance or depopulate specific rotational states. The angular momentum composition of the resulting wave packet, and the efficiency of the control scheme, is determined by calculating the multipulse response of the time-dependent Rydberg populations. DOI: 10.1103/PhysRevLett.91.243601 PACS numbers: 33.80.Rv Coherent control experiments in molecular systems have tended to employ complex waveforms [1][2][3][4] generated by feedback-controlled learning loops [5]. Despite the fact that they can be remarkably effective even in complex molecules [1][2][3]6] and biological systems [3], they are not intuitive and so it is difficult to unravel the underlying physics [6]. It is extremely tempting to try to control molecular processes from first principles and recognize the control mechanism. Ideal laboratories for the design of logical control schemes are Rydberg wave packets, since the phase parameters are readily determined. The relative phases of the interfering pathways are important since optical control processes rely on the interferences between different excitation pathways. Previous experiments controlling the dynamics of Rydberg electron wave packets have focused on simple atomic systems. Phase-shaped pulses have been employed to excite arbitrary wave packets [7] and to fully characterize their amplitude and phase profile [8][9][10]. Intuitive schemes exploiting trains of phase-locked optical pulses have been employed to create Schrö dinger's cat states [11], to demonstrate Young's double slit interference in an atom [12], to control electronic orbital angular momentum [13], and the radial distribution [14]. In this Letter, we take a step further and develop an intuitive scheme to control the dynamics of a molecular system. We explore the dynamics of a molecular electron wave packet composed predominantly of two Rydberg series belonging to two different rotational quantum states of the molecular ion. We determine the accumulated phase difference and deduce an intuitive pulse sequence to obtain full control over the time-dependent populations of the rotational quantum state of the wave packet.First, consider a wave packet composed of a superposition of two noninteracting Rydberg series, with different orbital angular momenta l and quantum defects l , converging to the same ionization limit. Such a wave packet may be considered as being composed of two separate components and is written r; t nl a nl nl r exp ÿi! nl t , where nl r is the radial wave function of the eigenstate jnli, ! nl ÿ1=2 n ÿ l 2 is its frequency and a nl is its amplitude in the superposition. After an integer number of orbit periods k, each wave packet, corresponding to a channel l, accumulates a phase 2 k l , resulting in an accumulated ph...

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“…In our own group, we have studied the intermediate Rydberg states of NO, with principal quantum number n = 25-35 in static and ramped external fields [32][33][34]. We have also investigated the dynamics of Rydberg electron wave packets in NO [35][36][37] and demonstrated that it is possible to control the composition of the wave packet by employing phase-locked pairs of optical pulses [1,2].…”

Section: Introductionmentioning

confidence: 99%

A spectroscopic investigation of the ionisation and dissociation decay dynamics of Rydberg states of NO

et al. 2014

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Double-resonance spectroscopy has been employed to characterise the autoionising and predissociating Rydberg states of NO converging to the υ + = 0 and υ + = 1 levels of the X 1 + ground state of NO + . Below the lowest ionisation limit, we monitor the formation of the N( 2 D) predissociation product and observe a spectrum dominated by the p(N + = 0) series, with smaller contributions from the p(2) and f(2) series. Many of the lineshapes can be fit to a simple Fano line profile. Upon vibrational excitation, a competing autoionisation channel is opened and we monitor the products of both the dissociation and ionisation channels. The υ + = 1 predissociation spectrum appears much more complex than the υ + = 0 predissociation spectrum, with significant contributions from the p(0), f(2), p(2), s (1) and d(1) series. In contrast, the υ + = 1 ionisation spectrum is dominated by the p(0) and f(2) Rydberg series, with much weaker contributions from s(1), d(1) and p(2) series. The lineshapes in the υ + = 1 predissociation and autoionisation spectra are perturbed and cannot be fit to simple Fano line profiles. In some extreme cases, these perturbations result in the complete disappearance of peaks from either the autoionisation or predissociation spectrum.

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The role of phase in molecular Rydberg wave packet dynamics

Cited by 16 publications

References 28 publications

VUV excitation of a vibrational wavepacket in D₂measured through strong-field dissociative ionization

VUV excitation of a vibrational wavepacket in D₂measured through strong-field dissociative ionization

Optical Control of the Rotational Angular Momentum of a Molecular Rydberg Wave Packet

A spectroscopic investigation of the ionisation and dissociation decay dynamics of Rydberg states of NO

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The role of phase in molecular Rydberg wave packet dynamics

Cited by 16 publications

References 28 publications

VUV excitation of a vibrational wavepacket in D2measured through strong-field dissociative ionization

VUV excitation of a vibrational wavepacket in D2measured through strong-field dissociative ionization

Optical Control of the Rotational Angular Momentum of a Molecular Rydberg Wave Packet

A spectroscopic investigation of the ionisation and dissociation decay dynamics of Rydberg states of NO

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Product

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VUV excitation of a vibrational wavepacket in D₂measured through strong-field dissociative ionization

VUV excitation of a vibrational wavepacket in D₂measured through strong-field dissociative ionization