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Electronic quantum coherence in glycine molecules probed with ultrashort x-ray pulses in real time.

ABSTRACT: Here, we use x-rays to create and probe quantum coherence in the photoionized amino acid glycine. The outgoing photoelectron leaves behind the cation in a coherent superposition of quantum mechanical eigenstates. Delayed x-ray pulses track the induced coherence through resonant x-ray absorption that induces Auger decay and by photoelectron emission from sequential double photoionization. Sinusoidal temporal modulation of the detected signal at early times (0 to 25 fs) is observed in both measurements. Advanced ab initio many-electron simulations allow us to explain the first 25 fs of the detected coherent quantum evolution in terms of the electronic coherence. In the kinematically complete x-ray absorption measurement, we monitor its dynamics for a period of 175 fs and observe an evolving modulation that may implicate the coupling of electronic to vibronic coherence at longer time scales. Our experiment provides a direct support for the existence of long-lived electronic coherence in photoionized biomolecules.

SUBMITTER: Schwickert D

PROVIDER: S-EPMC9159702 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

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Electronic quantum coherence in glycine molecules probed with ultrashort x-ray pulses in real time.

Schwickert David D Ruberti Marco M Kolorenč Přemysl P Usenko Sergey S Przystawik Andreas A Baev Karolin K Baev Ivan I Braune Markus M Bocklage Lars L Czwalinna Marie Kristin MK Deinert Sascha S Düsterer Stefan S Hans Andreas A Hartmann Gregor G Haunhorst Christian C Kuhlmann Marion M Palutke Steffen S Röhlsberger Ralf R Rönsch-Schulenburg Juliane J Schmidt Philipp P Toleikis Sven S Viefhaus Jens J Martins Michael M Knie André A Kip Detlef D Averbukh Vitali V Marangos Jon P JP Laarmann Tim T

Science advances 20220601 22

Here, we use x-rays to create and probe quantum coherence in the photoionized amino acid glycine. The outgoing photoelectron leaves behind the cation in a coherent superposition of quantum mechanical eigenstates. Delayed x-ray pulses track the induced coherence through resonant x-ray absorption that induces Auger decay and by photoelectron emission from sequential double photoionization. Sinusoidal temporal modulation of the detected signal at early times (0 to 25 fs) is observed in both measure ...[more]

PMID: 35648864

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Project description:The theory of electronic structure of many-electron systems, such as molecules, is extraordinarily complicated. A consideration of how electron density is distributed on average in the average field of the other electrons in the system, that is, mean field theory, is very instructive. However, quantitatively describing chemical bonds, reactions, and spectroscopy requires consideration of the way that electrons avoid each other while moving; this is called electron correlation (or in physics, the many-body problem for fermions). Although great progress has been made in theory, there is a need for incisive experimental tests for large molecular systems in the condensed phase. In this Account, we report a two-dimensional (2D) optical coherent spectroscopy that correlates the double-excited electronic states to constituent single-excited states. The technique, termed 2D double-quantum coherence spectroscopy (2D-DQCS), uses multiple, time-ordered ultrashort coherent optical pulses to create double- and single-quantum coherences over time intervals between the pulses. The resulting 2D electronic spectrum is a map of the energy correlation between the first excited state and two-photon allowed double-quantum states. The underlying principle of the experiment is that when the energy of the double-quantum state, viewed in simple models as a double HOMO-to-LUMO (highest occupied to lowest unoccupied molecular orbital) excitation, equals twice that of a single excitation, then no signal is radiated. However, electron-electron interactions, a combination of exchange interactions and electron correlation, in real systems generates a signal that reveals precisely how the energy of the double-quantum resonance differs from twice the single-quantum resonance. The energy shift measured in this experiment reveals how the second excitation is perturbed by both the presence of the first excitation and the way that the other electrons in the system have responded to the presence of that first excitation. We compare a series of organic dye molecules and find that the energy offset for adding a second electronic excitation to the system relative to the first excitation is on the order of tens of millielectronvolts; it also depends quite sensitively on molecular geometry. These results demonstrate the effectiveness of 2D-DQCS for elucidating quantitative information about electron-electron interactions, many-electron wave functions, and electron correlation in electronic excited states and excitons. Our work helps illuminate the implications of electron correlation on chemical systems. In a broad sense, we are trying to help address the fundamental question "How do we go beyond the orbital representation of electrons in the chemical sciences?"

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Electronic quantum coherence in glycine molecules probed with ultrashort x-ray pulses in real time.

Publications

Electronic quantum coherence in glycine molecules probed with ultrashort x-ray pulses in real time.

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