Internal rotation in dimethylacetylene

The vibrational spectrum of dimethyl acetylene has been remeasured with better resolving power than hitherto, and the rotational fine structure of some perpendicular type bands has been partly analyzed. The energy levels of a molecule of this kind in which internal rotation of methyl groups may arise have been re-examined theoretically and the rotational structure of the absorption bands has been more clearly defined than previously. The experimental results are consistent with the assumption of unrestricted internal rotation of the methyl groups, and the Coriolis factors $\zeta _{i}$ for several vibrations have been determined.

Ultrafast excited state dynamics controlling photochemical isomerization of N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium coordinated to a {Re-1(CO)(3)(2,2 '-bipyridine)} chromophore

Two Multifunctional photoactive complexes [Re(Cl)(CO)(3)-(MeDpe(+))(2)](2+) and [Re(MeDpe(+))(CO)(3)(bpy)](2+) (MeDpe(+) = N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium, bpy = 2,2'-bipyridine) were synthesized. characterized. and their redox and photonic properties were investigated by cyclic voltammetry: ultraviolet-visible-infrared (UV/Vis/IR) spectroelectrochemistry, stationary UV/Vis and resonance Raman spectroscopy; photolysis; picosecond time-resolved absorption spectroscopy in the visible and infrared regions: and time-resolved resonance Raman spectroscopy. The first reduction step of either complex Occurs at about -1.1 V versus Fc/Fc(+) and is localized at MeDpe(+). Reduction alone does not induce a trans -> cis isomerization of MeDpe(+). [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) is photostable, while [Re(MeDpe(+))(CO)(3)(bpy)](2+) and free MeDpe(+) isomerize under near-UV irradiation. The lowest excited state of [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) has been identified as the Re(Cl)(CO)(3) -> MeDpe(+) (MLCT)-M-3 (MLCT = metal-to-ligand charge transfer), decaying directly to the ground state with lifetimes of approximate to 42 (73%) and approximate to 430ps (27%). Optical excitation of [Re(MeDpe(+))(CO)(3)(bpy)](2+) leads to population of Re(CO)(3) -> MeDpe(+) and Re(CO)(3) -> bpy (MLCT)-M-3 states, from which a MeDpe(+) localized intraligand 3 pi pi* excited state ((IL)-I-3) is populated with lifetimes of approximate to 0.6 and approximate to 10 ps, respectively. The 3IL state undergoes a approximate to 21 ps internal rotation, which eventually produces the cis isomer on a much longer timescale. The different excited-state behavior of the two complexes and the absence of thermodynamically favorable interligand electron transfer in excited [Re(MeDpe(+))(CO)(3)(bpy)](2+) reflect the fine energetic balance between excited states of different orbital origin, which can be tuned by subtle Structural variations. The complex [Re(MeDpe+)(CO)(3)(bpy)](2+) emerges as a prototypical, multifunctional species with complementary redox and photonic behavior.

A calibrated, non-invasive method for measuring the internal interface height field at high resolution in the rotating, two-layer annulus

We describe a remote sensing method for measuring the internal interface height field in a rotating, two-layer annulus laboratory experiment. The method is non-invasive, avoiding the possibility of an interaction between the flow and the measurement device. The height fields retrieved are accurate and highly resolved in both space and time. The technique is based on a flow visualization method developed by previous workers, and relies upon the optical rotation properties of the working liquids. The previous methods returned only qualitative interface maps, however. In the present study, a technique is developed for deriving quantitative maps by calibrating height against the colour fields registered by a camera which views the flow from above. We use a layer-wise torque balance analysis to determine the equilibrium interface height field analytically, in order to derive the calibration curves. With the current system, viewing an annulus of outer radius 125 mm and depth 250 mm from a distance of 2 m, the inferred height fields have horizontal, vertical and temporal resolutions of up to 0.2 mm, 1 mm and 0.04 s, respectively.

Independent component analysis of climate data: A new look at EOF rotation

The complexity inherent in climate data makes it necessary to introduce more than one statistical tool to the researcher to gain insight into the climate system. Empirical orthogonal function (EOF) analysis is one of the most widely used methods to analyze weather/climate modes of variability and to reduce the dimensionality of the system. Simple structure rotation of EOFs can enhance interpretability of the obtained patterns but cannot provide anything more than temporal uncorrelatedness. In this paper, an alternative rotation method based on independent component analysis (ICA) is considered. The ICA is viewed here as a method of EOF rotation. Starting from an initial EOF solution rather than rotating the loadings toward simplicity, ICA seeks a rotation matrix that maximizes the independence between the components in the time domain. If the underlying climate signals have an independent forcing, one can expect to find loadings with interpretable patterns whose time coefficients have properties that go beyond simple noncorrelation observed in EOFs. The methodology is presented and an application to monthly means sea level pressure (SLP) field is discussed. Among the rotated (to independence) EOFs, the North Atlantic Oscillation (NAO) pattern, an Arctic Oscillation–like pattern, and a Scandinavian-like pattern have been identified. There is the suggestion that the NAO is an intrinsic mode of variability independent of the Pacific.

Comparison of subcellular partitioning, distribution, and internal speciation of Cu between Cu-tolerant and naive populations of Dendrodrilus rubidus Savigny

When considering contaminated site ecology and ecological risk assessment a key question is whether organisms that appear unaffected by accumulation of contaminants are tolerant or resistant to those contaminants. A population of Dendrodrilus rubidus Savigny earthworms from the Coniston Copper Mines, an area of former Cu mining, exhibit increased tolerance and accumulation of Cu relative to a nearby non-Cu exposed population. Distribution of total Cu between different body parts (posterior, anterior, body wall) of the two populations was determined after a 14 day exposure to 250 mg Cu kg(-1) in Cu-amended soil. Cu concentrations were greater in Coniston earthworms but relative proportions of Cu in different body parts were the same between populations. Cu speciation was determined using extended X-ray absorption fine structure spectroscopy (EXAFS). Cu was coordinated to 0 atoms in the exposure soil but to S atoms in the earthworms. There was no difference in this speciation between the different earthworm populations. In another experiment earthworms were exposed to a range of Cu concentrations (200-700 mg Cu kg(-1)). Subcellular partitioning of accumulated Cu was determined. Coniston earthworms accumulated more Cu but relative proportions of Cu in the different fractions (cytosol > granular > tissue fragments, cell membranes, and intact cells) were the same between populations. Results suggest that Coniston D. rubidus are able to survive in the Cu-rich Coniston Copper Mines soil through enlargement of the same Cu storage reservoirs that exist in a nearby non-Cu exposed population.

Anharmonic force constant calculations

The relationship of the anharmonic force constants in curvilinear internal coordinates to the observed vibration-rotation spectrum of a molecule is reviewed. A simplified method of setting up the required non-linear coordinate transformations is described: this makes use of an / tensor, which is a straightforward generalization of the / matrix used in the customary description of harmonic force constant calculations. General formulae for the / tensor elements, in terms of the familiar L matrix elements, are presented. The use of non-linear symmetry coordinates and redundancies are described. Sample calculations on the water and ammonia molecules are reported.

Vibration-rotation spectra of CH3F

Rotational structure has been resolved and analyzed in the 1049-cm−1 parallel fundamental and the 1182 cm−1 perpendicular fundamental bands in the infrared spectrum of the CH3F molecule. Combination bands at 2223 cm−1 and around 2650 cm−1 have also been studied. The effective resolving power of the spectrometer was 0.25 cm−1 for all these bands. The two long-wavelength fundamentals have been analyzed in much greater detail than in previous work, and a complete analysis of the perpendicular band has been made, including the J-structure in the P and R branches of the sub-bands. Rotational constants of CH3F determined in this work and elsewhere are summarized in Table XIII of the text. Some anomalous intensity perturbations in the rotation lines of the 1182-cm−1 fundamental have been observed, and are discussed.

Vibration-rotation spectra of monofluoroacetylene: 1700 to 7500 cm−1

High-resolution vibration-rotation spectra of monofluoroacetylene are reported for many bands in the region 1700 to 7500 cm−1. The spectra were observed on Nicolet 7199 and Bruker IFS 120 Fourier spectrometers, with resolutions of about 0.06 and 0.003 cm−1, respectively. About 130 bands have been observed in this region, of which about 80 have been rotationally analyzed. The assignment of vibrational labels to the higher energy levels is complicated by the effects of strong Fermi resonances, and many weak localized rotational resonances are observed.

Raman selection rules for vibration-rotation transitions in symmetric top molecules

Symmetry restrictions on Raman selection rules can be obtained, quite generally, by considering a Raman allowed transition as the result of two successive dipole allowed transitions, and imposing the usual symmetry restrictions on the dipole transitions. This leads to the same results as the more familiar polarizability theory, but the vibration-rotation selection rules are easier to obtain by this argument. The selection rules for symmetric top molecules involving the (+l) and (-l) components of a degenerate vibrational level with first-order Coriolis splitting are derived in this paper. It is shown that these selection rules depend on the order of the highest-fold symmetry axis Cn, being different for molecules with n=3, n=4, or n ≧ 5; moreover the selection rules are different again for molecules belonging to the point groups Dnd with n even, and Sm with 1/2m even, for which the highest-fold symmetry axes Cn and Sm are related by m=2n. Finally it is shown that an apparent anomaly between the observed Raman and infra-red vibration-rotation spectra of the allene molecule is resolved when the correct selection rules are used, and a value for the A rotational constant of allene is derived without making use of the zeta sum rule.

The two-dimensional anharmonic oscillator I: vibration-rotation constants of fulminic acid, HCNO

The lowest-wavenumber vibration of HCNO and DCNO, ν5, is known to involve a largeamplitude low-frequency anharmonic bending of the CH bond against the CNO frame. In this paper the anomalous vibrational dependence of the observed rotational constants B(v5, l5), and of the observed l-doubling interactions, is interpreted according to a simple effective vibration-rotation Hamiltonian in which the appropriate vibrational operators are averaged in an anharmonic potential surface over the normal coordinates (Q5x, Q5y). All of the data on both isotopes are interpreted according to a single potential surface having a minimum energy at a slightly bent configuration of the HCN angle ( 170°) with a maximum at the linear configuration about 2 cm−1 higher. The other coefficients in the Hamiltonian are also interpreted in terms of the structure and the harmonic and anharmonic force fields; the substitution structure at the “hypothetical linear configuration” determined in this way gives a CH bond length of 1.060 Å, in contrast to the value 1.027 Å determined from the ground-state rotational constants. We also discuss the difficulties in rationalizing our effective Hamiltonian in terms of more fundamental theory, as well as the success and limitations of its use in practice.

The infrared vibration-rotation spectrum of trans and cis nitrous acid

Infrared spectra of the trans and the cis isomers of nitrous acid, both HONO and DONO, have been observed in the gas phase using a Fourier transform interferometer with a resolution of about 0.05 cm−1 from 4000 to 500 cm−1. Rotational analyses are reported on eleven of the fundamentals and some overtones.