Reagents for electrophilic amination: a quantum Monte Carlo study

Electrophilic amination is an appealing synthetic strategy to construct carbon-nitrogen bonds. The authors explore the use of the quantum Monte Carlo method and a proposed variant of the electron pair localization function--the electron pair localization function density--as a measure of the nucleophilicity of nitrogen lone pairs as a possible screening procedure for electrophilic reagents.     

A Hollow Stiffening Structure for Low Pressure Sensors

This paper presents a novel process for producing thin-walled hollow stiffening structures on thin silicon diaphragms using an electro-chemical etch stop process. Examples of structures produced using the method are presented together with focused ion beam (FIB) analysis of critical areas within the structure. These demonstrate the integrity the structures and show that the process is it suitable for use in MEMS sensor applications. Using this process a 30mbar full-scale differential pressure sensor has been demonstrated. The process allows for increased sensor performance, with reduced die size. Details of the pressure sensor design and characterization are presented, showing a device with 20mV/V full-scale output with linearity less than 0.4% (terminal base nonlinearity).     

Matrix infrared spectroscopic and theoretical of the difluoroamino metal fluoride molecules: F2NMF (M = Cu, Ag, Au)

The difluoroamino coinage metal fluoride molecules F(2)NMF (M = Cu, Ag, Au) have been made via spontaneous reactions of coinage metals and NF(3) in solid argon and neon matrixes during sample annealing without formation of the M(NF(3)) complexes. Comparisons between the matrix infrared spectra and the density functional frequency calculations provide strong support for identification of the F(2)NMF molecules, which are found to have doublet ground states with C(2v) or near C(2v) geometries. The F(2)NCuF molecule can isomerize to the less stable FNCuF(2) isomer upon UV-visible irradiation, while no similar reactions were observed for the silver and gold species. The M-N bonds in the F(2)NMF molecules are stronger than those in the FNMF(2) isomers with the Ag-N bond being longest and weakest in both cases.     

Insights on the CN B 2Σ+ + Ar potential from ultraviolet fluorescence excitation and infrared depletion studies of the CN-Ar complex

UV laser-induced fluorescence and IR-UV fluorescence depletion studies have been used to characterize the intermolecular levels of the CN-Ar complex in the excited state correlating with CN B (2)Σ(+) + Ar. Additional CN-Ar features are identified to lower wavenumber than reported previously. Fluorescence depletion spectra are recorded to confirm that these CN-Ar features and other higher energy features in the B-X spectrum originate from a common ground state level. The UV depletion is induced by IR excitation of CN-Ar from the ground state zero-point level to a hindered internal rotor state (n(K) = 1(1)) in the CN overtone region. The lowest energy feature in the B-X spectrum at 25,714.1 cm(-1) is assigned as a transition to the zero-point level of the B state and also yields its binding energy, D(0) = 186(2) cm(-1), which is in excellent accord with theoretical predictions. The next feature approximately 40 cm(-1) higher is attributed to overlapping transitions to intermolecular levels with bend (v(b)(K)=1(1)) or stretch (v(s) = 1) excitation. Yet higher features (previously reported) are also assigned, based on their transition type and wavenumber, which are consistent with the intermolecular energy level pattern computed theoretically. Finally, the intensity profile of the lowest energy features in the B-X spectrum reflects the predicted change in the CN (B (2)Σ(+), X (2)Σ(+)) + Ar potentials upon electronic excitation from a weakly anisotropic potential about the linear N≡C-Ar configuration in the ground state to a more strongly bound linear C≡N-Ar structure in the excited B electronic state.     

STEREOELECTRONIC PROPERTIES OF PHOTOSYNTHETIC AND RELATED SYSTEMS—VIII. AB INITIO QUANTUM MECHANICAL CHARACTERIZATION OF THE ELECTRONIC STRUCTURE AND SPECTRUM OF THE BACTERIOPHEOPHORBIDE a ANION RADICAL

Ab initio configuration interaction wavefunctions and energies are reported for 16 doublet states of the anion radical of ethyl bacteriopheophorbide a (Et-BPheo a^-˙), and are employed in an analysis of the electronic absorption spectrum. The lowest excited doublet state D₁ is predicted to lie 8601 cm^-1 above the ground state D₀; the D₁← D₀ transition is nearly forbidden, with a computed oscillator strength f= 0.002. The visible absorption spectrum is shown to consist of transitions to three ²(π, π*) states, D₂, D₃, and D₄. The D₄← D₀ transition (y-polarized, f= 0.91) appears to account for observed intense absorption at 15 800 cm^-1. The Soret band of Et-BPheo a^-˙ is shown to consist of transitions to several ²(π,π*) states, D₇-D₁₅. Transitions of particularly high intensity include D₇← D₀ (y-polarized, f= 0.72), D₁₀← D₀ (y-polarized, f= 1.1), D₁₂← D₀ (xy-polarized, f= 0.86) and D₁₅← D₀ (y-polarized, f= 0.83). Spin density data and plots are used to describe and compare the general features of the unpaired spin distributions in D₀ and D₁, which are in reasonable agreement with other reported calculated values and available experimental data for D₀.     

Fluorescence spectrum of the benzene radical cation in solid argon

Argon/benzene samples were condensed at 12 K with continuous argon resonance radiation. Laser excitation at 421 nm produced a weak emission with structure at 19770, 19140 and 18290 cm^?1, assigned to the ²A_2u → ²E_1g emission of C₆H₆⁺. Observation of 630 and 1480 cm^?1 intervals for the vibrations v₁₈ (e_2g) and v₆ (e_2g), respectively, supports this assignment.     

Frequency and effects of teachers'' voice problems

This study compared the frequency and effects of voice symptomsin teachers to a group of individuals employed in other occupations. Teachers were more likely to report having a voice problem (15 vs. 6%), having 10 specific voice symptoms, and having 5 symptoms of physical discomfort. They averaged almost 2 symptoms compared with none for nonteachers. Likewise, teachers were more likely to perceive that a voice problem would adversely affect their future career options, had done so in the past, and was limiting their current job performance. Over 20% of teachers but none of the nonteachers had missed any days of work due to a voice problem. These findings suggest that teaching is a high-risk occupation for voice disorders and that this health problem may have significant work-related and economic effects.     

The electronic absorption and magnetic circular dichroism spectra of IrBr6 2- in several host crystals

The absorption and magnetic circular dichroism (M.C.D.) spectrum of the IrBr₆ ^2- ion at room and liquid helium temperature has been studied in the host crystals (NH₄)₂SnBr₆, K₂SnBr₆ and (C₂H₅NH₃)₂SnBr₆ in the region ～11 000–21 000 cm^-1. An interpretation of the spectrum is presented which differs significantly from those suggested previously. In order of increasing energy the allowed bands are assigned to the following ligand-to-metal charge-transfer transitions: E_g ″(² T _2g )→ U_u ′(² T _1u ) (13–14 000 cm^-1), E_g ″(² T _2g )→ E_u ″(² T _2u ) (16 800 cm^-1), and E_g ″(² T _2g )→ U_u ′(² T _2u ) (～ 18 300 cm^-1). Both our absorption and M.C.D. data strongly suggest a Jahn-Teller splitting of the U_u ′(² T _1u ) state but contradict a previous suggestion of such a splitting of the U_u ′(² T _2u ) state. Consideration of σ—π mixing in the t _1u (π + σ) molecular orbital suggests that the ～17 300 cm^-1 band arises from the orbitally-forbidden E_g ″(² T _2g )→ E_u ′(² T _1u ) transition. Bands in the 11 000–13 000 cm^-1 region are assigned to parity-forbidden charge-transfer transitions to states generated by the t _1g (π)→ t _2g excitation. The fine structure seen at liquid helium temperature in K₂SnBr₆ : Ir⁴⁺ both in the 14 500 cm^-1 band and overlying the E_g ″→ U_u ′(² T _2u ) band appears to be associated with parity-forbidden transitions.     

Far-infrared giant dipole resonances in neutral quantum dots

A resonance behaviour of the far-infrared absorption probability at a frequency N^1/4 is predicted for clusters of N electron–hole pairs (2N110) confined in disk-shaped quantum dots. For radially symmetric dots, the absorption is dominated by a giant dipole resonance, which accounts for more than 98% of the energy-weighted photoabsorption sum rule.     

Elastic moduli of random network models of amorphous Ge and Si

The bulk and shear moduli of periodic random network models of amorphous Ge and Si are computed. The Young's modulus is reduced to about 90% of the average in the crystalline form.