Multiple Wavelength Extinction Technique for Particle Characterization in Dense Particle Clouds

In utilizing the advantages of extinction measurements in micron and especially submicron particle characterization, the properties of a multiple wavelength extinction technique have been the subject of extended theoretical studies. Furthermore, an experimental set-up was designed which provides high flexibility owing to its modular design. The performance of the technique described is demonstrated by a large variety of applications in aerosol and combustion research and in large-scale industrial systems. It was found to be a reliable tool in characterizing dense particulate systems.     

Two-frequency two-photon ionization of nascent PO(X2II) from the collision-free IR photolysis of dimethyl methylphosphonate

We report the detection of nascent PO produced via the collision-free IR photolysis of dimethyl methylphosphonate. Absorption throughout the B²Σ⁺ ← X²Π system is followed by excitation using 266 nm radiation, which results in PO⁺ + e. Spectral features due to spin-orbit excitation appear extremely “cold” relative to vibrations and rotations.     

Modalities and quantum mechanics

Three approaches concerning the usage of modalities in the language of quantum mechanics were considered; Mittelstaedt and I built up a dialog semantics for modalities on a metalinguistic level, and a calculus of quantum modal logic is known that is complete and sound with respect to this dialogic semantics. Van Fraassen replaced the usual interpretation of quantum mechanics (with the projection postulate) by his modal interpretation based on a modal object language. Dalla Chiara translated a nonmodal object language for quantum mechanics and the appropriate quantum logic into a modal language. Specifically we are interested in the similarities and the differences of these three approaches.     

On the ultraviolet photodissociation of H(2)Te

The photodissociation of H(2)Te through excitation in the first absorption band is investigated by means of multireference spin-orbit configuration interaction (CI) calculations. Bending potentials for low-lying electronic states of H(2)Te are obtained in C(2v) symmetry for Te-H distances fixed at the ground state equilibrium value of 3.14a(0), as well as for the minimum energy path constrained to R(1)=R(2). Asymmetric cuts of potential energy surfaces for excited states (at R(1)=3.14a(0) and theta;=90.3 degrees ) are obtained for the first time. It is shown that vibrational structure in the 380-400 nm region of the long wavelength absorption tail is due to transitions to 3A('), which has a shallow minimum at large HTe-H separations. Transitions to this state are polarized in the molecular plane, and this state converges to the excited TeH((2)Pi(1/2))+H((2)S) limit. These theoretical data are in accord with the selectivity toward TeH((2)Pi(1/2)) relative to TeH((2)Pi(3/2)) that has been found experimentally for 355 nm H(2)Te photodissociation. The calculated 3A(')<--XA(') transition dipole moment increases rapidly with HTe-H distance; this explains the observation of 3A(') vibrational structure for low vibrational levels, despite unfavorable Franck-Condon factors. According to the calculated vertical energies and transition moment data, the maximum in the first absorption band at approximately 245 nm is caused by excitation to 4A("), which has predominantly 2(1)A(") ((1)B(1) in C(2v) symmetry) character.     

Asymmetric allylboration of alpha,beta-enals as a surrogate for the enantioselective synthesis of allylic amines and alpha-amino acids

[reaction: see text] Optically pure allylic amines have been synthesized from alpha,beta-unsaturated aldehydes via allylboration with (-)-B-allyldiisopinocampheylborane, followed by Overman rearrangement. By incorporating crotyl and alkoxyallylboration, functionalization at delta-position was readily accomplished. By applying this methodology, the synthesis of several chiral alpha-amino acids has been achieved.     

Heavy hydrides: H2Te ultraviolet photochemistry

The room-temperature ultraviolet absorption spectrum of H2Te has been recorded. Unlike other group-6 hydrides, it displays a long-wavelength tail that extends to 400 nm. Dissociation dynamics have been examined at photolysis wavelengths of 266 nm (which lies in the main absorption feature) and 355 nm (which lies in the long-wavelength tail) by using high-n Rydberg time-of-flight spectroscopy to obtain center-of-mass translational energy distributions for the channels that yield H atoms. Photodissociation at 355 nm yields TeH(2Pi1/2) selectively relative to the TeH(2Pi3/2) ground state. This is attributed to the role of the 3A' state, which has a shallow well at large R(H-TeH) and correlates to H+TeH(2Pi1/2). Note that the 2Pi1/2 state is analogous to the 2P1/2 spin-orbit excited state of atomic iodine, which is isoelectronic with TeH. The 3A' state is crossed at large R only by 2A", with which it does not interact. The character of 3A' at large R is influenced by a strong spin-orbit interaction in the TeH product. Namely, 2Pi1/2 has a higher degree of spherical symmetry than does 2Pi3/2 (recall that I(2P1/2) is spherically symmetric), and consequently 2Pi1/2 is not inclined to form either strongly bonding or antibonding orbitals with the H atom. The 3A'<--X transition dipole moment dominates in the long-wavelength region and increases with R. Structure observed in the absorption spectrum in the 380-400 nm region is attributed to vibrations on 3A'. The main absorption feature that is peaked at approximately 240 nm might arise from several excited surfaces. On the basis of the high degree of laboratory system spatial anisotropy of the fragments from 266 nm photolysis, as well as high-level theoretical studies, the main contribution is believed to be due to the 4A" surface. The 4A"<--X transition dipole moment dominates in the Franck-Condon region, and its polarization is in accord with the experimental observations. An extensive secondary photolysis (i.e., of nascent TeH) is observed at 266 and 355 nm, and the corresponding spectral features are assigned. Analyses of the c.m. translational energy distributions yield bond dissociation energies D0. For H2Te and TeH, these are 65.0+/-0.1 and 63.8+/-0.4 kcalmol, respectively, in good agreement with predictions that use high-level relativistic theory.     

SYNTHESIS OF CHIRAL THIOCARBAMOYLPHOSPHINES DERIVED FROM AMINO ACIDS1

Abstract

The methylester hydrochlorides of the (S)-amino acids L-alanine (la), L-phenylalanine (1b), L-valine (1c) and L-lysine (1d) were converted to the corresponding isothiocyanates 2a-d by thiophosgenation. 2a-d react with secondary phosphines and phosphine oxides to give the thiocarbamoylphosphines 3a-d and P-oxides 4a, b.