Probing the Structure, Pseudorotation, and Radial Vibrations of Cyclopentane by Femtosecond Rotational Raman Coherence Spectroscopy

Femtosecond time-resolved Raman rotational coherence spectroscopy (RCS) is employed to determine accurate rotational, vibration–rotation coupling constants, and centrifugal distortion constants of cyclopentane (C⁵H¹⁰). Its lowest-frequency vibration is a pseudorotating ring deformation that interconverts 10 permutationally distinct but energetically degenerate “twist” minima interspersed by 10 “bent” conformers. While the individual twist and bent structures are polar asymmetric tops, the pseudorotation is fast on the time scale of external rotation, rendering cyclopentane a fluxionally nonpolar symmetric top molecule. The pseudorotational level pattern corresponds to a one-dimensional internal rotor with a pseudorotation constant Bps ≈ 2.8 cm⁻¹. The pseudorotational levels are significantly populated up to l = ± 13 at 298 K; <10% of the molecules are in the l = 0 level. The next-higher vibration is the “radial” ν²³ ring deformation mode at 273 cm⁻¹, which is far above the pseudorotational fundamental. Femtosecond Raman RCS measurements were performed in a gas cell at T = 293 K and in a pulsed supersonic jet at T ≈ 90 K. The jet cooling reduces the pseudorotational distribution to l < ±8 and eliminates the population of ν²³, allowing one to determine the rotational constant as A0 = B0 = 6484.930(11) MHz. This value is ∼300 times more precise than the previous value. The fit of the RCS transients reveals that the rotation–pseudorotation coupling constant αe,psB = −0.00070(1) MHz is diminutive, implying that excitation of the pseudorotation has virtually no effect on the B0 rotational constant of cyclopentane. The smallness of αe,psB can be realized when comparing to the vibration–rotation coupling constant of the ν²³ vibration, αe,23B = −9.547(1) MHz, which is about 10⁴ times larger.

Rotational constants and structure of para-difluorobenzene determined by femtosecond Raman coherence spectroscopy: A new transient type

Femtosecond Raman rotational coherence spectroscopy (RCS) detected by degenerate four-wave mixing is a background-free method that allows to determine accurate gas-phase rotational constants of non-polar molecules. Raman RCS has so far mostly been applied to the regular coherence patterns of symmetric-top molecules, while its application to nonpolar asymmetric tops has been hampered by the large number of RCS transient types, the resulting variability of the RCS patterns, and the 10³–10⁴ times larger computational effort to simulate and fit rotational Raman RCS transients. We present the rotational Raman RCS spectra of the nonpolar asymmetric top 1,4-difluorobenzene (para-difluorobenzene, p-DFB) measured in a pulsed Ar supersonic jet and in a gas cell over delay times up to ~2.5 ns. p-DFB exhibits rotational Raman transitions with ΔJ = 0, 1, 2 and ΔK = 0, 2, leading to the observation of J −, K −, A −, and C–type transients, as well as a novel transient (S–type) that has not been characterized so far. The jet and gas cell RCS measurements were fully analyzed and yield the ground-state (v = 0) rotational constants Aₒ = 5637.68(20) MHz, Bₒ = 1428.23(37) MHz, and Cₒ = 1138.90(48) MHz (1σ uncertainties). Combining the Aₒ, Bₒ, and Cₒ constants with coupled-cluster with single-, double- and perturbatively corrected triple-excitation calculations using large basis sets allows to determine the semi-experimental equilibrium bond lengths rₑ(C₁–C₂) = 1.3849(4) Å, rₑ(C₂–C³) = 1.3917(4) Å, rₑ(C–F) = 1.3422(3) Å, and rₑ(C₂–H₂) = 1.0791(5) Å.

European expert consensus on rotational atherectomy

The interest in rotational atherectomy (RA) has increased over the past decade as a consequence of more complex and calcified coronary stenoses being attempted with percutaneous coronary interventions. Yet adoption of RA is hampered by several factors: amongst others, by the lack of a standardised protocol. This European expert consensus document stems from the awareness of the large heterogeneity in the protocols adopted to perform rotational atherectomy. The objective of the present document is to provide some points of consensus among highly experienced operators on the most controversial steps of RA in an attempt to build the basis of a standardised and universally accepted protocol.

Rotations, Precursor to Rotational Spectroscopy, and Group Theory

Rotations are an integral part of the study of rotational spectroscopy, as well as a part of group theory, hence this introduction.

Seasonal and Rotational Influences on Corn Nitrogen Requirements

This project is designed to study the N fertilization needs in continuous corn (CC) and corn rotated with soybean (SC) as influenced by location and climate. Multiple rates of fertilizer N are spring applied, with the intent to measure yield response to N within each rotation on a yearly basis for multiple years at multiple sites across Iowa. This will allow the determination of N requirements for each rotation, differences that exist between the two rotations, responses to applied N across different soils and climatic conditions, and evaluation of tools used to adjust N application.

Seasonal and Rotational Influences on Corn Nitrogen Requirements

This project was designed to study the N fertilization needs in continuous corn (CC) and corn rotated with soybean (SC) as influenced by location and climate. Multiple rates of fertilizer N were spring applied, with the intent to measure yield response to N within each rotation on a yearly basis for multiple years at multiple sites across Iowa. This will allow the determination of N requirements for each rotation, differences that exist between the two rotations, responses to applied N across different soils and climatic conditions, and evaluation of tools used to adjust N application.

Seasonal and Rotational Influences on Corn Nitrogen Requirements

This project was designed to study the N fertilization needs in continuous corn (CC) and corn rotated with soybean (SC) as influenced by location and climate. Multiple rates of fertilizer N were spring applied, with the intent to measure yield response to N within each rotation on a yearly basis for multiple years at multiple sites across Iowa. This will allow determination of N requirements for each rotation, differences that exist between the two rotations, responses to applied N across different soils and climatic conditions, and evaluation of tools used to adjust N application.

Seasonal and Rotational Influences on Corn Nitrogen Requirements

This project was designed to study the N fertilization needs in continuous corn (CC) and corn rotated with soybean (SC) as influenced by location and climate. Multiple rates of fertilizer N were spring applied, with the intent to measure yield response to N within each rotation on a yearly basis for multiple years at multiple sites across Iowa. This will allow the determination of N requirements for each rotation, differences that exist between the two rotations, responses to applied N across different soils and climatic conditions, and evaluation of tools used to adjust N application.

Dynamic Response of Wind Turbines to Theoretical 3D Seismic Motions Taking into Account the Rotational Component

We study the dynamic response of a wind turbine structure subjected to theoretical seismic motions, taking into account the rotational component of ground shaking. Models are generated for a shallow moderate crustal earthquake in the Madrid Region (Spain). Synthetic translational and rotational time histories are computed using the Discrete Wavenumber Method, assuming a point source and a horizontal layered earth structure. These are used to analyze the dynamic response of a wind turbine, represented by a simple finite element model. Von Mises stress values at different heights of the tower are used to study the dynamical structural response to a set of synthetic ground motion time histories

Measurement of velocity in rotational flows using ultrasonic anemometry: the flowmeter

In this paper a previously developed theoretical model of the measurement process performed by a transit-time ultrasonic anemometer is applied to a fluid flowing through a circular section pipe. This model considers the influence of the shift of the acoustic pulse trajectory from straight propagation due to the flow on the measured speed. The aim of this work is to estimate the errors induced in the measured velocity by the shift of the acoustic pulse trajectory. Using different duct’s flow models, laminar and turbulent regimes have been analyzed. The results show that neglecting the effect of shift of the acoustic pulse trajectory leads to flow rate measurement underestimation.

Deviations of cup anemometer rotational speed measurements due to steady state harmonic accelerations of the rotor

The measurement deviations of cup anemometers are studied by analyzing the rotational speed of the rotor at steady state (constant wind speed). The differences of the measured rotational speed with respect to the averaged one based on complete turns of the rotor are produced by the harmonic terms of the rotational speed. Cup anemometer sampling periods include a certain number of complete turns of the rotor, plus one incomplete turn, the residuals from the harmonic terms integration within that incomplete turn (as part of the averaging process) being responsible for the mentioned deviations. The errors on the rotational speed due to the harmonic terms are studied analytically and then experimentally, with data from more than 500 calibrations performed on commercial anemometers.

Factors controlling the competition among rotational and vibrational energy transfer channels in glyoxal

The state-to-state transfer of rotational and vibrational energy has been studied for S1 glyoxal (CHOCHO) in collisions with D2, N2, CO and C2H4 using crossed molecular beams. A laser is used to pump glyoxal seeded in He to its S1 zero point level with zero angular momentum about its top axis (K′ = 0). The inelastic scattering to each of at least 26 S1 glyoxal rotational and rovibrational levels is monitored by dispersed S1–S0 fluorescence. Various collision partners are chosen to investigate the relative influences of reduced mass and the collision pair interaction potential on the competition among the energy transfer channels. When the data are combined with that obtained previously from other collision partners whose masses range from 2 to 84 amu, it is seen that the channel competition is controlled primarily by the kinematics of the collisional interaction. Variations in the intermolecular potential play strictly a secondary role.

Visualization of a peripheral stalk in V-type ATPase: Evidence for the stator structure essential to rotational catalysis

F- and V-type ATPases are central enzymes in energy metabolism that couple synthesis or hydrolysis of ATP to the translocation of H+ or Na+ across biological membranes. They consist of a soluble headpiece that contains the catalytic sites and an integral membrane-bound part that conducts the ion flow. Energy coupling is thought to occur through the physical rotation of a stalk that connects the two parts of the enzyme complex. This mechanism implies that a stator-like structure prevents the rotation of the headpiece relative to the membrane-bound part. Such a structure has not been observed to date. Here, we report the projected structure of the V-type Na+-ATPase of Clostridium fervidus as determined by electron microscopy. Besides the central stalk, a second stalk of 130 Å in length is observed that connects the headpiece and membrane-bound part in the periphery of the complex. This additional stalk is likely to be the stator.

Changing nucleosome positions through modification of the DNA rotational information.

The effects of the rotational information of DNA in determining the in vitro localization of nucleosomal core particles (ncps) have been studied in the Saccharomyces cerevisiae 5S rRNA repeat gene. We have altered the distribution of the phased series of flexibility signals present on this DNA by inserting a 25-bp tract, and we have analyzed the effects of this mutation on the distribution and on the frequencies of ncps, as compared with the wild type and a reference 21-bp insertion mutant. The variation of the standard free energy of nucleosome reconstitution was determined. The results show that the DNA rotational information is a major determinant of ncps positioning, define how many rotationally phased signals are required for the formation of a stable particle, and teach how to modify their distribution through the alteration of the rotational signals.

Fluctuation analysis of rotational speeds of the bacterial flagellar motor.

We measured the dependence of the variance in the rotation rate of tethered cells of Escherichia coli on the mean rotation rate over a regime in which the motor generates constant torque. This dependence was compared with that of broken motors. In either case, motor torque was augmented with externally applied torque. We show that, in contrast to broken motors, functioning motors in this regime do not freely rotationally diffuse and that the variance measurements are consistent with the predicted values of a stepping mechanism with exponentially distributed waiting times (a Poisson stepper) that steps approximately 400 times per revolution.