Modulated Noncollinear Optical Parametric Amplifier Output Induced by Stimulated Raman Scattering

We studied spectra of the amplified signal from a noncollinear optical parametric amplifier (NOPA) based on a Ti:sapphire laser and BBO crystal gain medium. The signal shows characteristic structures with periodic intensity variations in the signal during the parametric amplification processes in a BBO crystal. This phenomenon is attributed to the stimulated Raman process excited by the pump pulse affected by the phase-matching condition of four-wave mixing. The effect of this stimulated Raman process on optical parametric amplification and on final pulse compression of the signal was analyzed. The results demonstrate that caution must be taken when constructing a NOPA. Specifically, great care must be taken not to use mirrors with non-uniform spectral reflectivity for obtaining a stable pulse in terms of both temporal and spectral shapes.

Chiral or Luminescent Lanthanide Single-Molecule Magnets Involving Bridging Redox Active Triad Ligand

The reactions between the bis(1,10-phenantro[5,6-b])tetrathiafulvalene triad (L) and the metallo-precursors Yb(hfac)3(H2O)2 (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonato anion) and Dy(facam)3 (facam− = 3-trifluoro-acetyl-(+)-camphorato anion) lead to the formation of two dinuclear complexes of formula [Yb2(hfac)6(L)]·2(C7H16) ((1)·2(C7H16)) and [Dy2((+)facam)6(L)]·2(C6H14) ((2)·2(C6H14)). The X-ray structures reveal that the L triad bridges two terminal Yb(hfac)3 or Dy(facam)3 units. (1)·2(C7H16) behaved as a near infrared YbIII centered emitter and a field-induced Single-Molecule Magnet (SMM) while (2)·2(C6H14) displayed SMM behavior in both zero- and in-dc field. The magnetization mainly relaxes through a Raman process for both complexes under an optimal applied magnetic field.

Near-Infrared Emissive Cyanido-Bridged {YbFe2} Molecular Nanomagnets Sensitive to the Nitrile Solvents of Crystallization

One of the pathways toward luminescent single-molecule magnets (SMMs) is realized by the self-assembly of lanthanide(3+) ions with cyanido transition metal complexes. We report a novel family of emissive SMMs, {YbIII(4-pyridone)4[FeII(phen)2(CN)2]2}(CF3SO3)3·solv (solv = 2MeCN, 1·MeCN; 2AcrCN, 1·AcrCN; 2PrCN, 1·PrCN; 2MalCN·1MeOH; 1·MalCN; MeCN = acetonitrile, AcrCN = acrylonitrile, PrCN = propionitrile, MalCN = malononitrile). They are based on paramagnetic YbIII centers coordinating diamagnetic [FeII(phen)2(CN)2] metalloligands but differ in the nitrile solvents of crystallization. They exhibit a field-induced slow magnetic relaxation dominated by a Raman process, without an Orbach relaxation as indicated by AC magnetic data and the ab initio calculations. The Raman relaxation is solvent-dependent as represented by the power “n” of the BRamanTn contribution varying from 3.07(1), to 2.61(1), 2.37(1), and 1.68(4) for 1·MeCN, 1·PrCN, 1·AcrCN, and 1·MalCN, respectively, while the BRaman parameter adopts the opposite trend. This was correlated with the variation of phonon modes schemes, including the number of available vibrational modes and their energies, dependent on the increasing complexity of the applied nitrile. 1·MeCN and 1·MalCN show the additional T-independent relaxation assignable to dipole-dipole interactions as confirmed by its suppression in 1·AcrCN and 1·PrCN revealing longer Yb–Yb distances and the disappearance in the LuIII-diluted 1·MeCN@Lu. All compounds exhibit YbIII–centered near-infrared photoluminescence sensitized by organic ligands.

Field-Induced Single-Molecule Magnets of Dysprosium Involving Quinone Derivatives

The coordination reaction of the [Dy(hfac)3(H2O)2] units (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonate) with the two quinone-based derivatives 4,7-di-tert-butyl-2-(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)benzo[d][1,3]dithiole-5,6-dione (L1) and 7,8-dithiabicyclo[4.2.0]octa-1,5-diene-3,4-dione,2,5bis(1,1-dimethylethyl) (L2) led respectively to the complexes [Dy(hfac)3(H2O)(L1)] (1) and [Dy(hfac)3(H2O) (L2)]⋅(C6H14)(CH2Cl2) (2)⋅(C6H14)(CH2Cl2). X-ray structures on single crystal of 1 and 2⋅(C6H14)(CH2Cl2) revealed the coordination of the DyIII on the bischelating oxygenated quinone site and the formation of dimeric species through hydrogen bonds. Ac magnetic measurements highlighted field-induced single-molecule magnet behavior with magnetic relaxation through a Raman process.

Quantum Optimal Control of Rovibrational Excitations of a Diatomic Alkali Halide: One-Photon vs. Two-Photon Processes

We investigated the roles of one-photon and two-photon processes in the laser-controlled rovibrational transitions of the diatomic alkali halide, 7Li37Cl. Optimal control theory calculations were carried out using the Hamiltonian, including both the one-photon and two-photon field-molecule interaction terms. Time-dependent wave packet propagation was performed with both the radial and angular motions being treated quantum mechanically. The targeted processes were pure rotational and vibrational–rotational excitations: (v = 0, J = 0) → (v = 0, J = 2); (v = 0, J = 0) → (v = 1, J = 2). Total time of the control pulse was set to 2,000,000 atomic units (48.4 ps). In each control excitation process, weak and strong optimal fields were obtained by means of giving weak and strong field amplitudes, respectively, to the initial guess for the optimal field. It was found that when the field is weak, the control mechanism is dominated exclusively by a one-photon process, as expected, in both the targeted processes. When the field is strong, we obtained two kinds of optimal fields, one causing two-photon absorption and the other causing a Raman process. It was revealed, however, that the mechanisms for strong fields are not simply characterized by one process but rather by multiple one- and two-photon processes. It was also found that in the rotational excitation, (v = 0, J = 0) → (v = 0, J = 2), the roles of one- and two-photon processes are relatively distinct but in the vibrational–rotational excitation, (v = 0, J = 0) → (v = 1, J = 2), these roles are ambiguous and the cooperative effect associated with these two processes is quite large.