Vibronic spectroscopy of unsaturated transition metal complexes: CrC2H, CrCH3, and NiCH3

Vibronically resolved resonant two-photon ionization and dispersed fluorescence spectra of the organometallic radicals CrC(2)H, CrCH(3), and NiCH(3) are reported in the visible and near-infrared wavelength regions. For CrC(2)H, a complicated vibronic spectrum is found in the 11 100-13 300 cm(-1) region, with a prominent vibrational progression having omega(e) (')=426.52+/-0.84 cm(-1), omega(e) (')x(e) (')=0.74+/-0.13 cm(-1). Dispersed fluorescence reveals a v(")=1 level of the ground state with DeltaG(1/2) (")=470+/-20 cm(-1). These vibrational frequencies undoubtedly pertain to the Cr-C(2)H stretching mode. It is suggested that the spectrum corresponds to the A (6)Sigma(+)<--X (6)Sigma(+) band system, with the CrC(2)H molecule being linear in both the ground and the excited state. The related CrCH(3) molecule displays a vibronic spectrum in the 11 500-14 000 cm(-1) region. The upper state of this system displays six sub-bands that are too closely spaced to be vibrational structure, but too widely separated to be K structure. It is suggested that the observed spectrum is a (6)E<--X (6)A(1) band system, analogous to the well-known B (6)Pi<--X (6)Sigma(+) band systems of CrF and CrCl. The ground state Cr-CH(3) vibration is characterized by omega(e) (")=525+/-17 cm(-1) and omega(e) (")x(e) (")=7.9+/-6 cm(-1). The spectrum of NiCH(3) lies in the 16 100-17 400 cm(-1) range and has omega(e) (')=455.3+/-0.1 cm(-1) and omega(e) (')x(e) (')=6.60+/-0.03 cm(-1). Dispersed fluorescence studies provide ground state vibrational constants of omega(e) (")=565.8+/-1.6 cm(-1) and omega(e) (")x(e) (")=1.7+/-3.0 cm(-1). Again, these values correspond to the Ni-CH(3) stretching motion. (c) 2004 American Institute of Physics.     

Correspondence on “Scoring Rules for Subjective Assessments”

Journal of the Operational Research Society -     

Negative group velocity Lamb waves on plates and applications to the scattering of sound by shells

Symmetric Lamb waves on plates exhibit anomalies for certain regions of frequency. The phase velocity appears to be double-valued [M. F. Werby and H. Uberall, J. Acoust. Soc. Am. 111, 2686-2691 (2002)] with one of the branches having a negative group velocity relative to the corresponding phase velocity. The classification of the symmetric plate modes for frequencies appearing to have a double-valued phase velocity is reviewed here. The complication of a double-valued velocity is avoided by examining mode orthogonality and the complex wave-number spectra. Various authors have noted an enhancement in the backscattering of sound by elastic shells in water that occurs for frequencies where symmetric leaky Lamb waves (generalized to case of a shell) have contra-directed group and phase velocities. The ray diagram for negative group velocity contributions to the scattering by shells [G. Kaduchak, D. H. Hughes, and P. L. Marston, J. Acoust. Soc. Am. 96, 3704-3714 (1994)] is unusual since for this type of mode the energy on the shell flows in the opposite direction of the wave vector. Circumnavigation of the shell is not required for the leaky ray to be backward directed.     

New method of measuring electric dipole moments in storage rings

A new highly sensitive method of looking for electric dipole moments of charged particles in storage rings is described. The major systematic errors inherent in the method are addressed and ways to minimize them are suggested. It seems possible to measure the muon EDM to levels that test speculative theories beyond the standard model.     

High strain gradient plasticity associated with wedge indentation into face-centered cubic single crystals: Geometrically necessary dislocation densities

Experimental studies on indentation into face-centered cubic (FCC) single crystals such as copper and aluminum were performed to reveal the spatially resolved variation in crystal lattice rotation induced due to wedge indentation. The crystal lattice curvature tensors of the indented crystals were calculated from the in-plane lattice rotation results as measured by electron backscatter diffraction (EBSD). Nye's dislocation density tensors for plane strain deformation of both crystals were determined from the lattice curvature tensors. The least L²-norm solutions to the geometrically necessary dislocation densities for the case in which three effective in-plane slip systems were activated in the single crystals associated with the indentation were determined. Results show the formation of lattice rotation discontinuities along with a very high density of geometrically necessary dislocations.     

Negative axial radiation forces on solid spheres and shells in a Bessel beam

Prior computations predict that fluid spheres illuminated by an acoustic Bessel beam can be subjected to a radiation force directed opposite the direction of beam propagation. The prediction of negative acoustic radiation force is extended to the cases of a solid poly(methylmethacrylate) PMMA sphere in water and an empty aluminum spherical shell in water. Compared with the angular scattering patterns for plane wave illumination, the scattering into the back hemisphere is suppressed when the radiation force is negative. This investigation may be helpful in the development of acoustic tweezers and in the development of methods for manipulating objects during space flight.     

Spin-forbidden c 3Sigma1+<--X 1Sigma+ band system of YF

Optical spectra of jet-cooled diatomic YF have been recorded using resonant two-photon ionization spectroscopy. A vibrational progression corresponding to the c 3Sigma1+<--X 1Sigma+ system has been identified. The vibrational frequency omegae' and anharmonicity omegae'xe' of the c 3Sigma+ state are 546.70 and 2.45 cm-1, respectively. The 0-0, 1-0, and 2-0 bands of the c 3Sigma1+<--X 1Sigma+ system were rotationally resolved and analyzed, allowing the v'=0, 1, and 2 levels of the c 3Sigma1+ substate to be characterized. From these studies, Be'=0.269 81(3) cm-1, alphae'=0.001 72(3) cm-1, and re'=1.9979(1) A were obtained (1sigma error limits). For these levels the spin-spin coupling constant lambdav is identical within experimental error, as lambda=-22.5 cm-1. The spin-forbidden c 3Sigma1+<--X 1Sigma+ transition is made allowed by spin-orbit interaction between the c 3Sigma1+ and the B 1Pi states. Excited state lifetimes of the c 3Sigma1+ and the B 1Pi states have been measured as 7.11(41) and 0.133(15) micros, respectively. A spin-orbit analysis shows that the c 3Sigma1+ state is contaminated with 2% B 1Pi character, which is approximately sufficient to explain the 7 micros lifetime of the c 3Sigma1+ state.     

Brownian dynamics algorithm for entangled wormlike threads

The authors present a hybrid Brownian dynamics/Monte Carlo algorithm for simulating solutions of highly entangled semiflexible polymers or filaments. The algorithm combines a Brownian dynamics time-stepping approach with an efficient scheme for rejecting moves that cause chains to cross or that lead to excluded volume overlaps. The algorithm allows simulation of the limit of infinitely thin but uncrossable threads, and is suitable for simulating the conditions obtained in experiments on solutions of long actin protein filaments.     

Rotationally resolved spectroscopy of jet-cooled NbMo

Rotationally resolved resonant two-photon ionization spectra of jet-cooled NbMo are reported for the first time. A vibronic spectrum of NbMo was recorded in the 17 300-22 300 cm(-1) spectral region. Although the observed bands could not be grouped into electronic band systems, four excited vibronic levels with Omega=2.5 and two excited levels with Omega=3.5 were identified. The ground state of NbMo has been assigned as (2)Delta(52), deriving from a 1sigma(2)1pi(4)1delta(3)2sigma(2) configuration of the valence electrons. Rotational analysis of six bands provides a ground state rotational constant of B(0) (")=0.087 697(26) cm(-1), corresponding to a bond length of r(0) (")=2.008 09(30) A for (93)Nb(98)Mo. Correction for the effects of the spin-uncoupling operator changes the estimated bond length only slightly to r(0) (")=2.008 02(30) A. The experimentally determined value of r(0) (") is compared to that predicted using previously determined multiple bonding radii of Nb and Mo. A comparison to the known diatomic molecules composed of group V and VI metal atoms is also made.     

Influence of surfactant upon air entrainment hysteresis in curtain coating

The onset of air entrainment for curtain coating onto a pre-wetted substrate was studied experimentally in similar parameter regimes to commercial coating (Re = ρQ/μ = O(1), We = ρQ u _c /σ = O(10), Ca = μU/σ = O(1)). Impingement speed and viscosity were previously shown to be critical parameters in correlating air entrainment data with three qualitatively different regimes of hydrodynamic assist identified (Marston et al. in Exp Fluids 42(3):483–488, 2007a). The interaction of the impinging curtain with the pre-existing film also led to a significant hysteretic effect throughout the flow rate-substrate speed parameter space. For the first time, results considering the influence of surfactants are presented in attempt to elucidate the relative importance of surface tension in this inertia-dominated system. The results show quantitative and qualitative differences to previous results with much more complex hysteretic behaviour which has only been reported previously for rough surfaces.