Direct observation of nonclassical photon statistics in parametric down-conversion

We employ a high quantum efficiency photon number counter to determine the photon number distribution of the output field from a parametric down-converter. The raw photocount data directly demonstrates that the source is nonclassical by 40 standard deviations, and correcting for the quantum efficiency yields a direct observation of oscillations in the photon number distribution.     

Entanglement formation and violation of Bell's inequality with a semiconductor single photon source

We report the generation of polarization-entangled photons, using a quantum dot single photon source, linear optics, and photodetectors. Two photons created independently are observed to violate Bell's inequality. The density matrix describing the polarization state of the postselected photon pairs is reconstructed and agrees well with a simple model predicting the quality of entanglement from the known parameters of the single photon source. Our scheme provides a method to create no more than one entangled photon pair per cycle after postselection, a feature useful to enhance quantum cryptography protocols based on shared entanglement.     

Enhanced diastereoselectivity via confinement: diastereoselective photoisomerization of 2,3-diphenyl-1-benzoylcyclopropane derivatives within zeolites

Photochemistry of optically pure trans-2,3-diphenyl-1-benzoylcyclopropane has been examined in isotropic solution and within zeolites. Results suggest that it isomerizes by cleavage of either the C1-C2 or C1-C3 bond. From the perspective of chiral induction, photoisomerization of cis-2,3-diphenyl-1-benzoylcyclopropane derivatives with chiral auxiliaries placed at the meta and para positions of the benzoyl group have been examined both in isotropic solution and within zeolites. Whereas in isotropic solution the chiral auxiliaries placed at the meta position exhibit very little influence during the conversion of triplet cis-2,3-diphenyl-1-benzoylcyclopropane derivatives, they have significant influence within zeolites. For example, alpha-methyl benzylamine placed at the meta position of the benzoyl group (via an amide bond) yields the trans isomer with a diastereoselectivity (de) of 71% within NaY zeolite, whereas in solution no de is obtained. The chiral induction process within zeolites depends on the nature of the alkali ion and on the presence of water. Results suggest that the chiral auxiliary is able to control the bond being cleaved (C1-C2 vs. C1-C3 bond) within a zeolite, but it is unable to do so in an isotropic solution.     

Intramolecular nonbonded S?O interaction in acetazolamide and thiadiazolinethione molecules in their dimeric crystalline structures and complex crystalline structures with enzymes

The dimeric crystalline structure of acetazolamide 1 and thiadiazolinethione 2 bearing intramolecular nonbonded S?O interactions, in each different hydrogen-bonding manner was clarified by their X-ray crystallographic analysis. Existence of the dimeric structure of 1 and 2 in a MeOH solution could be suggested on the basis of their cold-spray ionization mass spectrometry. The intramolecular nonbonded S?O interaction was precisely recognized in the complex crystalline structures of carbonic anhydrase I inhibitor 1 and stromelysin inhibitors 2-4 with each specific enzyme. The computational evaluation of the possible monomeric seven conformers of 1 and two model compounds 5 and 6 of 2-4 based on DFT calculations defined that the conformer bearing the intramolecular nonbonded S?O interaction is most stable.     

Mediation of conformationally controlled photodecarboxylations of chiral and cyclic aryl esters by substrate structure, temperature, pressure, and medium constraints

An aryl alkanoate, 2,4,6-trimethylphenyl (S)-(+)-2-methylbutyrate, whose ester group has a chiral center alpha to the carbonyl carbon and in which photo-Fries rearrangements are blocked by methyl substituents, undergoes facile photodecarboxylation under a variety of conditions and with complete retention of configuration. In fact, the decarboxylation process has many of the attributes of a symmetry-allowed suprafacial [1,3]sigmatropic rearrangement. The process requires concerted extrusion of carbon dioxide in a spiro-lactonic transition state, which has been investigated using high level DFT and CIS calculations: thermally less stable s-cis conformers in the ground and excited singlet states play an important role in determining the competitive efficiency of the process. Conformational control has also been imposed by substrate structure, solvent interactions, temperature, and applying external pressure, as well as using constraining media such as cyclodextrins and polyethylene films. The results are correlated with steady-state and dynamic fluorescence measurements at various temperatures in order to investigate further degrees to which ground and excited singlet state conformations affect the different photoreactivity channels available to the aryl esters.     

Diastereoselective [2 + 2] photocycloaddition of stilbene to chiral fumarate. Direct versus charge-transfer excitation

The selective excitation of the charge-transfer (CT) complex and the direct excitation of the substrate gave distinctly different product ratios and diastereomeric excesses (de's), as well as their temperature dependencies, in [2 + 2] photocycloaddition of (E)-stilbene to bis((R)-1-methylpropyl) fumarate, clearly demonstrating that the excited CT complex and the conventional exciplex differ in structure and reactivity. This conclusion is supported by the contrasting fluorescence behavior exhibited by the relevant excited species, particularly at low temperatures.     

Controlling the spontaneous emission rate of single quantum dots in a two-dimensional photonic crystal

We observe large spontaneous emission rate modification of individual InAs quantum dots (QDs) in a 2D photonic crystal with a modified, high-Q single-defect cavity. Compared to QDs in a bulk semiconductor, QDs that are resonant with the cavity show an emission rate increase of up to a factor of 8. In contrast, off-resonant QDs indicate up to fivefold rate quenching as the local density of optical states is diminished in the photonic crystal. In both cases, we demonstrate photon antibunching, showing that the structure represents an on-demand single photon source with a pulse duration from 210 ps to 8 ns. We explain the suppression of QD emission rate using finite difference time domain simulations and find good agreement with experiment.     

Highly efficient single-photon detection at communication wavelengths by use of upconversion in reverse-proton-exchanged periodically poled LiNbO3 waveguides

Conventional single-photon detectors at communication wavelengths suffer from low quantum efficiencies and large dark counts. We present a single-photon detection system, operating at communication wavelengths, based on guided-wave frequency upconversion in a nonlinear crystal with an overall system detection efficiency (upconversion + detection) exceeding 46% at 1.56 microm. This system consists of a fiber-pigtailed reverse-proton-exchanged periodically poled LiNbO3 waveguide device in conjunction with a silicon-based single-photon counting module.     

Complexation and chiral recognition thermodynamics of gamma-cyclodextrin with N-acetyl- and N-carbobenzyloxy-dipeptides possessing two aromatic rings

The stability constants (K) and the standard free energy (deltaG degrees ), enthalpy (deltaH degrees ), and entropy changes (deltaS degrees ) for the complexation of gamma-cyclodextrin with 34 enantiomeric and diastereomeric N-acetyl- and N-carbobenzyloxy-d/l-dipeptides with two aromatic moieties were determined in aqueous buffer solution at 298.15 K by titration microcalorimetry. Chiral recognition of the enantiomeric dipeptide pairs by gamma-cyclodextrin was found to be fairly poor, exhibiting only small percentage differences in K, while the diastereomeric dipeptides were discriminated to much greater extent with affinity differences of up to 6-7 times. The complex structures of several selected pairs were elucidated by NMR techniques. Combining the microcalorimetric and NMR data, the complexation and chiral recognition behavior of gamma-cyclodextrin is discussed in particular in terms of the length, bulkiness, and flexibility of the tether connecting the two aromatic moieties in a guest.