Theory of the Zeeman effect in doublet states of a near-symmetric rotor: Application to the A2 ← B1 transition of ClO2

Matrix elements of the Hamiltonian for doublet states of rotating molecules in a Zeeman field are calculated in the uncoupled (J, S) representation. The energy matrix assumes a simple form for near-symmetric rotors, when the magnetic interactions are diagonal in K.     

Ab initio dynamics study of poly-para-phenylene vinylene

We present an ab initio dynamics investigation within a density-functional perturbation theory framework of the properties of the conjugated polymer poly-para-phenylene vinylene (PPV) in both the isolated chain and crystalline states. The calculated results show that for an isolated chain, most of the vibrational modes correspond to experimentally observed modes in crystalline PPV. However, additional hitherto unidentified modes have been observed in experiment and our calculations on crystalline material have allowed us to assign these. We also present the results of calculations of the polarizability and permittivity tensors of the material, which are in reasonable agreement with the typical values for conjugated polymers. Dynamical Born effective charges [S. Baroni, S. de Gironcoli, A. Dal Corso, and P. Giannozzi, Rev. Mod. Phys. 73, 515 (2001)] are calculated and compared with atomic charges obtained from Mulliken population analysis [M. D. Segall, C. J. Pickard, R. Shah, and M. C. Payne, Mol. Phys. 89, 571 (1996)] and we conclude that effective charges are more appropriate for use in the study of the dynamics of the system. Notable differences are found in the infrared-absorption spectra obtained for the isolated chain and crystalline states, which can be attributed to the differences in the crystalline packing effects, which clearly play a key role in influencing the lattice dynamics of PPV.     

Nitrosation of sugar oximes: preparation of 2-glycosyl-1-hydroxydiazene-2-oxides

Oximes of glucose, xylose, lactose, fructose, and mannose have been prepared. Nitrosation of the oximes of glucose, xylose, and lactose with NaNO2/HCl afforded 2-(beta-glycopyranosyl)-1-hydroxydiazene-2-oxides, which were isolated as salts 13, 22, and 28. Nitrosation of fructose oxime 29 furnished fructose, whereas nitrosation of mannose oxime 30 with NaNO2/HCl afforded the 1-hydroxy-2-(beta-D-mannopyranosyl)diazene-2-oxide 32, from which the p-anisidinium salt 31 and the sodium salt 33 were prepared. However, nitrosation of 30 with isopentyl nitrite in aqueous solutions of CsOH or KOH resulted in the formation of the 2-(alpha-D-mannofuranosyl)-1-hydroxydiazene-2-oxide salts 34 and 35, respectively. Methylation of the ammonium 2-(beta-D-glucopyranosyl)-1-hydroxydiazene-2-oxide 13 yielded the 1-methoxy compound, which was benzoylated to afford the tetra-O-benzoate 14a, the structure of which was confirmed by X-ray diffraction analysis. From the glucose O-methyloximes 15 and 16 the N-methoxy-N-nitroso-2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosylamine 18 was prepared. The structure of this compound was confirmed by X-ray diffraction analysis. Treatment of acetobromoglucose with cupferron furnished the 1-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyloxy)-2-phenyldiazene-2-oxide 20.     

Electrical resistivity of heusler alloys

The electrical resistivity of eight different Heusler alloys is discussed in terms of electron phonon and spin-disorder scattering. The systematics common to the alloys can be explained in the intermediate to high temperature range while the low temperature range still presents interpretation difficulties.     

The two-photon spectrum of toluene vapor

The two-photon excitation spectrum of toluene-h₈ and toluene-d₈ vapor has been recorded under low resolution (1 cm^?1) in the region of the S₁ ← S₀ (¹B₂ ← ¹A₁) transition. Although the electronic transition is formally allowed in two-photon spectroscopy, a large fraction of intensity exists in a subsystem induced by the out-of-phase CC stretching vibration ν₁₄ (b₂). Band contours associated with each of the two assigned tensor components of the transition are identified and partially analyzed by comparison with the two-photon contours of fluorobenzene.     

The 3B1-1A1 band system of sulfur dioxide: Rotational analysis of the (010), (100), and (110) bands

The (010)-(000) band of the ${}^3\text{B}{}_1\text{←}{}^1\text{A}{}_1$ system of sulfur dioxide has been rotationally analyzed and constants for the magnetic interactions in the (010) vibrational level determined. Partial rotational analyses are given for the rotationally perturbed (100)-(000) and (110)-(000) bands of the system. The extensive perturbations in this band system are provisionally attributed to: (i) vibronic interaction with a ³A₂ state, visible (a) as a large negative anharmonicity in higher bands of the ³B₁ system, and (b) as a ΔK = 0 resonance perturbation in low-lying vibrational levels of the ³B₁ state; and (ii) a K, K ± 1N-dependent perturbation possibly due to rotational-electronic coupling with a ³B₂ state, though evidence on this point is incomplete. Evidence bearing on these conclusions is discussed.     

Pattern propagation in nonlinear dissipative systems

We discuss the problem of pattern selection in situations where a stable, nonuniform state of a nonlinear dissipative system propagates into an initially unstable, homogeneous region. Our strategy is to consider this process as a generalization of front propagation in a nonlinear diffusion problem for which rigorous results are known; and we point out that these known properties are consistent with a marginal-stability hypothesis that has been suggested in the theory of dendritic crystal growth. We then describe a more general interpretation of the marginal-stability hypothesis and, finally, present numerical evidence for its validity from three different pattern-forming models.     

Nanosecond relaxation dynamics of protein GB1 identified by the time-dependent red shift in the fluorescence of tryptophan and 5-fluorotryptophan

The B1 domain of Streptococcal protein G (GB1) is a small, thermostable protein containing a single tryptophan residue. We recorded time-resolved fluorescence of the wild-type GB1 and its 5-fluorotryptophan (5FTrp) variant at more than 30 emission wavelengths between 300 and 470 nm. The time-resolved emission spectra reveal no signs of heterogeneity, but show a time-dependent red shift characteristic of microscopic dielectric relaxation. This is true for both 5FTrp and unmodified Trp in GB1. The time-dependent red shifts in the fluorescence of 5FTrp and unmodified Trp are essentially identical, confirming that the shift is caused by the relaxation of the protein matrix rather than by the fluorophore itself. The total amplitude (but not the rate) of the time-dependent red shift depends on the fluorophore, specifically, on the magnitude of the vector difference between its excited state and ground state electric dipole moments; for 5FTrp this is estimated to be about 88% of that for the unmodified Trp. The decay of the excited state fluorophore population is not monoexponential for either fluorophore; however, the deviation from the monoexponential decay law is larger in the case of unmodified Trp. The relaxation dynamics of GB1 was found to be considerably faster than that of other proteins studied previously, consistent with the small size, tightly packed core, and high thermodynamic stability of GB1.     

Friction and diffusion of matter-wave bright solitons

We consider the motion of a matter-wave bright soliton under the influence of a cloud of thermal particles. In the ideal one-dimensional system, the scattering process of the quasiparticles with the soliton is reflectionless; however, the quasiparticles acquire a phase shift. In the realistic system of a Bose-Einstein condensate confined in a tight waveguide trap, the transverse degrees of freedom generate an extra nonlinearity in the system which gives rise to finite reflection and leads to dissipative motion of the soliton. We calculate the velocity and temperature-dependent frictional force and diffusion coefficient of a matter-wave bright soliton immersed in a thermal cloud.