Masahiro Kitagawa

Molecular electron-spin quantum computers and quantum information processing: pulse-based electron magnetic resonance spin technology applied to matter spin-qubits

Pulse-based Electron–Nuclear and ELectron–electron DOuble Resonance (ENDOR/ELDOR) techniques have been applied to molecular spins in order to implement ensemble electron spin-qubit based quantum computers/computing (QC) and quantum information processing (QIP) in the solid state. Pulsed ENDOR-based QC/QIP experiments for super dense coding (SDC) have for the first time been carried out by the use of molecular electron- and nuclear-spin entities such as the stable malonyl radical as matter spin-qubits. The spin-qubit manipulation technology for quantum gate operations in this work is based on the time-proportional-phase-increment (TPPI) technique, enabling us to distinguish between the phases of spin-qubit based entangled states. The TPPI technique, as firstly applied by Mehring et al. (M. Mehring, J. Mende and W. Scherer, Phys. Rev. Lett., 2003, 90, 153001), has illustrated the establishment of quantum entanglement between electron- and nuclear-spin states and mutual interconversion between the electron–nuclear Bell states. The electron-spin 4π-periodicity in phase shows up in the QC/QIP experiments, explicitly and experimentally illustrating the electron-spin spinor nature for the first time. Tripartite QC experiments have been made, showing the occurrence of separable states. Also, the development of novel electron-spin technology to manipulate multi-electron spin-qubits is described. In this work, the pulsed coherent-dual ELDOR for QC/QIP has for the first time been implemented by invoking a novel microwave dual phase-rotation technique. Thus, applications of the coherent-dual ELDOR to molecular electron spin-qubit systems are also discussed, emphasising designing the molecular two electron-qubit systems appropriate for QC/QIP. g- and/or hyperfine A-tensor engineering approaches give us the two- and multi-electron-qubit systems, which have been a materials challenge to implement matter spin-qubit based QC/QIP. The targeted matter spin-qubits can be used to facilitate selective resonant microwave excitations achieved by the pulsed ELDOR technique. In addition to DiVincenzos five criteria, general requisites for scalable electron spin-qubit systems as 1D periodic robust spin structures are described. According to the requisites, double- or triple-stranded helicates embedding open-shell metal cations are proposed instead of organic molecular spin-qubits.

A Synthetic Two-Spin Quantum Bit: g-Engineered Exchange-Coupled Biradical Designed for Controlled-NOT Gate Operations†

A quantum gate: A system of two coupled electron spins that is useful for simple quantum computing operations has been prepared by synthesis of a biradical 1 and co-crystallization with an isomorphous host molecule. The two weakly exchange-coupled quantum bits (target qubit blue and control qubit red) span four electron spin states. The electron spin transition is denoted by two black arrows.

Room temperature hyperpolarization of nuclear spins in bulk

Significance Nuclear spins are only slightly aligned even in the strong magnetic fields of superconducting magnets because the magnetic energy of nuclear spin is much smaller than thermal energy. This is the major reason for the low sensitivity of NMR spectroscopy. Using electron spins in thermal equilibrium, which have 660 times higher magnetic energy, the sensitivity can be enhanced by at most this factor through a method called dynamic nuclear polarization. Utilizing photo-excited nonthermalized electrons instead, we demonstrate an enhancement factor of 250,000 at room temperature, which can be applied to a wide range of fields including NMR, MRI, and physics. Dynamic nuclear polarization (DNP), a means of transferring spin polarization from electrons to nuclei, can enhance the nuclear spin polarization (hence the NMR sensitivity) in bulk materials at most 660 times for 1H spins, using electron spins in thermal equilibrium as polarizing agents. By using electron spins in photo-excited triplet states instead, DNP can overcome the above limit. We demonstrate a 1H spin polarization of 34%, which gives an enhancement factor of 250,000 in 0.40 T, while maintaining a bulk sample (∼0.6 mg, ∼0.7 × 0.7 × 1 mm3) containing >1019 1H spins at room temperature. Room temperature hyperpolarization achieved with DNP using photo-excited triplet electrons has potentials to be applied to a wide range of fields, including NMR spectroscopy and MRI as well as fundamental physics.

Spin-Orbit Contributions in High-Spin Nitrenes/Carbenes: A Hybrid CASSCF/MRMP2 Study of Zero-Field Splitting Tensors

Zero-field splitting (ZFS) tensors (D tensors) of organic high-spin oligonitrenes/oligocarbenes up to spin-septet are quantitatively determined on the basis of quantum chemical calculations. The spin-orbit contributions, D(SO) tensors are calculated in terms of a hybrid CASSCF/MRMP2 approach, which was recently proposed by us. The spin-spin counterparts, D(SS) tensors are computed based on McWeeny-Mizunos equation in conjunction with the RODFT spin densities. The present calculations show that more than 10% of ZFS arises from spin-orbit interactions in the high-spin nitrenes under study. Contributions of spin-bearing site-site interactions are estimated with the aid of a semi-empirical model for the D tensors and found to be ca. 5% of the D(SO) tensor. The analysis of intermediate states reveal that the largest contributions to the calculated D(SO) tensors are attributed to intra-site spin flip excitations and delocalized π and π* orbitals play an important role in the inter-site spin-orbit interactions.

Optimization of 1H spin density for dynamic nuclear polarization using photo-excited triplet electron spins.

In dynamic nuclear polarization (DNP) using photo-excited triplet electron spins, known as Microwave-Induced Optical Nuclear Polarization (MIONP), the attainable (1)H polarization is determined by the ratio of the buildup rate and the spin-lattice relaxation rate, in turn depend on the (1)H spin density. It is shown that the final (1)H polarization can be enhanced by diluting the (1)H spins with partial deuteration. The DNP experiments are demonstrated in 0.05 mol% pentacene-doped p-terphenyl for various (1)H abundances. It is also shown that the (1)H spin diffusion coefficient can be determined by examining the initial buildup rate of (1)H polarization for various repetition rates of the DNP sequence.

Spin Squeezing and Decoherence Limit in Ramsey Spectroscopy

It is known that partially entangled state gives improved sensitivity of Ramsey spectroscopy in the presence of decoherence, whereas maximally entangled state gives no improvement. However it has been an open question whether the absolute limit in the improvement is attainable by optimal entanglement alone or via measurement optimization. In this Paper, we answer this question by showing that even sub-optimal entanglement generated by the simplest spin squeezing can asymptotically attain the absolute improvement with increasing number of atoms.

Active compensation of rf-pulse transients.

A new approach to compensate rf-pulse transients is proposed. Based on the idea of the response theory of a linear system, a formula is derived to obtain the required excitation voltage profile back from the intended target rf-pulse shape. The validity of the formula is experimentally confirmed by monitoring the rf-field created inside the sample coil with a pickup coil. Since this approach realizes accurate rf-pulse shapes without reducing the Q-factor of the tank circuit of the probe, it can be used not only to suppress the transient tail of the rf-pulse, but also as a general concept for accurate rf-pulsing.

Pulsed electron spin nutation spectroscopy of weakly exchange-coupled biradicals: a general theoretical approach and determination of the spin dipolar interaction

Weakly exchange-coupled biradicals have attracted much attention in terms of their DNP application in NMR spectroscopy for biological systems or the use of synthetic electron-spin qubits. Pulse-ESR based electron spin nutation (ESN) spectroscopy applied to biradicals is generally treated as transition moment spectroscopy from the theoretical side, illustrating that it is a powerful and facile tool to determine relatively short distances between weakly exchange-coupled electron spins. The nutation frequency as a function of the microwave irradiation strength ω(1) (angular frequency) for any cases of weakly exchange-coupled systems can be classified into three categories; D(12) (spin dipolar interaction)-driven, Δg-driven and ω(1)-driven nutation behaviour with the increasing strength of ω(1). For hetero-spin biradicals, Δg effects can be a dominating characteristic in the biradical nutation spectroscopy. Two-dimensional pulse-based electron spin nutation (2D-ESN) spectroscopy operating at the X-band can afford to determine small values of D(12) in weakly exchange-coupled biradicals in rigid glasses. The analytical expressions derived here for ω(1)-dependent nutation frequencies are based on only four electronic spin states relevant to the biradicals, while real biradical systems often have sizable hyperfine interactions. Thus, we have evaluated nuclear hyperfine effects on the nutation frequencies to check the validity of the present theoretical treatment. The experimental spin dipolar coupling of a typical TEMPO-based biradical 1, (2,2,6,6-tetra[((2)H(3))methyl]-[3,3-(2)H(2),4-(2)H(1),5,5-(2)H(2)]piperidin-N-oxyl-4-yl)(2,2,6,6-tetra[((2)H(3))methyl]-[3,3-(2)H(2),4-(2)H(1),5,5-(2)H(2),(15)N]piperidin-(15)N-oxyl-4-yl) terephthalate in a toluene glass, with a distance of 1.69 nm between the two spin sites is D(12) = -32 MHz (the effect of the exchange coupling J(12) is vanishing due to the homo-spin sites of 1, i.e.Δg = 0), while 0 < |J(12)|≦ 1.0 MHz as determined by simulating the random-orientation CW ESR spectra of 1. In addition, we have carried out Q-band pulsed ELDOR (ELectron-electron DOuble Resonance) experiments to confirm whether the obtained values for D(12) and J(12) are accurate. The distance is in a fuzzy region for the distance-measurements capability of the conventional, powerful ELDOR spectroscopy. The strong and weak points of the ESN spectroscopy with a single microwave frequency applicable to weakly exchange-coupled multi-electron systems are discussed in comparison with conventional ELDOR spectroscopy. The theoretical spin dipolar tensor and exchange interaction of the TEMPO biradical, as obtained by sophisticated quantum chemical calculations, agree with the experimental ones.

PULSED ENDOR-BASED QUANTUM INFORMATION PROCESSING

Pulsed Electron Nuclear DOuble Resonance (pulsed ENDOR) has been studied for realization of quantum algorithms, emphasizing the implementation of organic molecular entities with an electron spin and a nuclear spin for quantum information processing. The scheme has been examined in terms of quantum information processing. Particularly, superdense coding has been implemented from the experimental side and the preliminary results are represented as theoretical expectations.

Noncovalent Assembly of TEMPO Radicals Pair-wise Embedded on a DNA Duplex

We have synthesized and characterized a new G–G mismatch binding ligand containing a TEMPO radical. The two mismatch binding ligands cooperatively bound to the CGG/CGG triad and an apparent binding...