Butterfly hysteresis loop at non-zero bias field in antiferromagnetic molecular rings: cooling by adiabatic magnetization

At low temperatures, the magnetization of the molecular ferric wheel NaFe$_6$ exhibits a step at a critical field $B_c$ due to a field-induced level-crossing. By means of high-field torque magnetometry we observed a hysteretic behavior at the level-crossing with a characteristic butterfly shape which is analyzed in terms of a dissipative two-level model. Several unusual features were found. The non-zero bias field of the level-crossing suggests the possibility of cooling by adiabatic magnetization.Comment: 4 pages, 5 figures, REVTEX4, to appear in PR

Ferromagnetic coupling and magnetic anisotropy in molecular Ni(II) squares

We investigated the magnetic properties of two isostructural Ni(II) metal complexes [Ni4Lb8] and [Ni4Lc8]. In each molecule the four Ni(II) centers form almost perfect regular squares. Magnetic coupling and anisotropy of single crystals were examined by magnetization measurements and in particular by high-field torque magnetometry at low temperatures. The data were analyzed in terms of an effective spin Hamiltonian appropriate for Ni(II) centers. For both compounds, we found a weak intramolecular ferromagnetic coupling of the four Ni(II) spins and sizable single-ion anisotropies of the easy-axis type. The coupling strengths are roughly identical for both compounds, whereas the zero-field-splitting parameters are significantly different. Possible reasons for this observation are discussed.Comment: 7 pages, 7 figure

Shaping the Laser Control Landscape of a Hydrogen Transfer Reaction by Vibrational Strong Coupling. A Direct Optimal Control Approach

Controlling molecular reactivity by shaped laser pulses is a long-standing goal in chemistry. Here we suggest a direct optimal control approach which combines external pulse optimization with other control parameters arising in the upcoming field of vibro-polaritonic chemistry, for enhanced controllability The direct optimal control approach is characterized by a simultaneous simulation and optimization paradigm, meaning that the equations of motion are discretized and converted into a set of holonomic constraints for a nonlinear optimization problem given by the control functional. Compared with indirect optimal control this procedure offers great flexibility such as final time or Hamiltonian parameter optimization. Simultaneous direct optimal control (SimDOC) theory will be applied to a model system describing H-atom transfer in a lossy Fabry-P\'erot cavity under vibrational strong coupling conditions. Specifically, optimization of the cavity coupling strength and thus of the control landscape will be demonstrated

Electronic structure study by means of X-ray spectroscopy and theoretical calculations of the "ferric star" single molecule magnet

The electronic structure of the single molecule magnet system M[Fe(L)2]3*4CHCl3 (M=Fe,Cr; L=CH3N(CH2CH2O)2) has been studied using X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, soft X-ray emission spectroscopy, and density functional calculations. There is good agreement between theoretical calculations and experimental data. The valence band mainly consists of three bands between 2 eV and 30 eV. Both theory and experiments show that the top of the valence band is dominated by the hybridization between Fe 3d and O 2p bands. From the shape of the Fe 2p spectra it is argued that Fe in the molecule is most likely in the 2+ charge state. Its neighboring atoms (O,N) exhibit a magnetic polarisation yielding effective spin S=5/2 per iron atom, giving a high spin state molecule with a total S=5 effective spin for the case of M = Fe.Comment: Fig.2 replaced as it will appear in J. Chem. Phy

Lower critical field H_c1 and barriers for vortex entry in Bi_2Sr_2CaCu_2O_{8+delta} crystals

The penetration field H_p of Bi_2Sr_2CaCu_2O_{8+delta} crystals is determined from magnetization curves for different field sweep rates dH/dt and temperatures. The obtained results are consistent with theoretical reports in the literature about vortex creep over surface and geometrical barriers. The frequently observed low-temperature upturn of H_p is shown to be related to metastable configurations due to barriers for vortex entry. Data of the true lower critical field H_c1 are presented. The low-temperature dependence of H_c1 is consistent with a superconducting state with nodes in the gap function. [PACS numbers: 74.25.Bt, 74.60.Ec, 74.60.Ge, 74.72.Hs

Spin dynamics in molecular ring nanomagnets: Significant effect of acoustic phonons and magnetic anisotropies

The nuclear spin-lattice relaxation rate 1/T_1_ is calculated for magnetic ring clusters by fully diagonalizing their microscopic spin Hamiltonians. Whether the nearest-neighbor exchange interaction J is ferromagnetic or antiferromagnetic, 1/T_1_ versus temperature T in ring nanomagnets may be peaked at around k_B_T=|J| provided the lifetime broadening of discrete energy levels is in proportion to T^3^. Experimental findings for ferromagnetic and antiferromagnetic Cu^II^ rings are reproduced with crucial contributions of magnetic anisotropies as well as acoustic phonons.Comment: 5 pages with 5 figures embedded, to be published in J. Phys. Soc. Jpn. 75, No. 10 (2006

Model Exact Low-Lying States and Spin Dynamics in Ferric Wheels; Fe6_6 to Fe12_{12}

Using an efficient numerical scheme that exploits spatial symmetries and spin-parity, we have obtained the exact low-lying eigenstates of exchange Hamiltonians for ferric wheels up to Fe$_{12}$. The largest calculation involves the Fe$_{12}$ ring which spans a Hilbert space dimension of about 145 million for M$_s$=0 subspace. Our calculated gaps from the singlet ground state to the excited triplet state agrees well with the experimentally measured values. Study of the static structure factor shows that the ground state is spontaneously dimerized for ferric wheels. Spin states of ferric wheels can be viewed as quantized states of a rigid rotor with the gap between the ground and the first excited state defining the inverse of moment of inertia. We have studied the quantum dynamics of Fe$_{10}$ as a representative of ferric wheels. We use the low-lying states of Fe$_{10}$ to solve exactly the time-dependent Schr\"odinger equation and find the magnetization of the molecule in the presence of an alternating magnetic field at zero temperature. We observe a nontrivial oscillation of magnetization which is dependent on the amplitude of the {\it ac} field. We have also studied the torque response of Fe$_{12}$ as a function of magnetic field, which clearly shows spin-state crossover.Comment: Revtex, 24 pages, 8 eps figure

Magnetic Anisotropy in the Molecular Complex V15

We apply degenerate perturbation theory to investigate the effects of magnetic anisotropy in the magnetic molecule V15. Magnetic anisotropy is introduced via Dzyaloshinskii-Moriya (DM) interaction in the full Hilbert space of the system. Our model provides an explanation for the rounding of transitions in the magnetization as a function of applied field at low temperature, from which an estimate for the DM interaction is found. We find that the calculated energy differences of the lowest energy states are consistent with the available data. Our model also offers a novel explanation for the hysteretic nature of the time-dependent magnetization data.Comment: Final versio

The Role of Structural Flexibility in Plasmon Driven Coupling Reactions Kinetic Limitations in the Dimerization of Nitro Benzenes

Abstract The plasmon-driven dimerization of 4-nitrothiophenol (4NTP) to 4-4′-dimercaptoazobenzene (DMAB) is a testbed for understanding bimolecular photoreactions enhanced by nanoscale metals, in particular, regarding the relevance of electron transfer and heat transfer from the metal to the molecule. By adding a methylene group between the thiol bond and the nitrophenyl, structural flexibility is added to the reactant molecule. Time-resolved surface-enhanced Raman-spectroscopy proves that this (4-nitrobenzyl)mercaptan (4NBM) molecule has a larger dimerization rate and dimerization yield than 4NTP and higher selectivity toward dimerization. X-ray photoelectron spectroscopy and density functional theory calculations show that the electron transfer prefers activation of 4NTP over 4NBM. It is concluded that the rate limiting step of this plasmonic reaction is the dimerization step, which is dramatically enhanced by the additional flexibility of the reactant. This study may serve as an example for using nanoscale metals to simultaneously provide charge carriers for bond activation and localized heat for driving bimolecular reaction steps. The molecular structure of reactants can be tuned to control the reaction kinetics