Photogenerated Spin-Entangled Qubit (Radical) Pairs in DNA Hairpins: Observation of Spin Delocalization and Coherence

Jacob H. Olshansky, Matthew D. Krzyaniak, Ryan M. Young, Michael R Wasielewski

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The ability to prepare physical qubits in specific initial quantum states is a critical requirement for their use in quantum information science (QIS). Subnanosecond photoinduced electron transfer in a structurally well-defined donor-acceptor system can be used to produce an entangled spin qubit (radical) pair in a pure initial singlet state fulfilling this criterion. Synthetic DNA is a promising platform on which to build spin qubit arrays with fixed spatial relationships; therefore, we have prepared a series of DNA hairpins in which naphthalenediimide (NDI) is the chromophore/acceptor hairpin linker, variable-length diblock A- and G-tracts are intermediate donors, and a stilbenediether (Sd) is the terminal donor. Photoexcitation of NDI in these DNA hairpins generates high-yield, long-lived, entangled spin qubit pairs at 85 K, and time-resolved and pulse electron paramagnetic resonance (EPR) spectroscopies are used to probe their spin dynamics. Specifically, measurements of the distance-dependent dipolar coupling between the two spins are used to obtain the average spin qubit pair distance in the absence of the terminal Sd donor and reveal that one of the spins is fully delocalized across up to five adjacent guanines in a G-tract on the EPR time scale. We have recently shown that extensive spin hopping between degenerate sites accessible to one spin of the pair may result in spin decoherence. However, we observe a strong out-of-phase electron spin echo envelope modulation (OOP-ESEEM) signal from the NDI•--Sd•+ spin qubit pair in DNA hairpins showing that spin coherence is maintained across a 2 adenine A-tract followed by a 2-4 guanine G-tract as a result of rapid spin transport to Sd. These results demonstrate that pulse-EPR can manipulate coherent spin states in DNA hairpins, which is essential for quantum gate operations relevant to QIS applications.

Original languageEnglish
Pages (from-to)2152-2160
Number of pages9
JournalJournal of the American Chemical Society
Volume141
Issue number5
DOIs
Publication statusPublished - Feb 6 2019

Fingerprint

DNA
Observation
Electron Spin Resonance Spectroscopy
Information Science
Paramagnetic resonance
Information science
Guanine
Electrons
Spin dynamics
Photoexcitation
Adenine
Chromophores
Spectrum Analysis
Modulation
Spectroscopy
naphthalenediimide

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Photogenerated Spin-Entangled Qubit (Radical) Pairs in DNA Hairpins : Observation of Spin Delocalization and Coherence. / Olshansky, Jacob H.; Krzyaniak, Matthew D.; Young, Ryan M.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, Vol. 141, No. 5, 06.02.2019, p. 2152-2160.

Research output: Contribution to journalArticle

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