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.

Physical properties and elastic constants of ODP Holes 137-504B and 140-504B upper crustal rocks

Seismic velocities have been measured at confining pressures of 100 MPa and 600 MPa for sheeted dike samples recovered during Ocean Drilling Program Legs 137 and 140. The compressional- and shear-wave velocities show an increase with depth at Hole 504B, which is in sharp contrast to the atmospheric pressure velocity measurements performed as part of the shipboard analyses. Rocks exposed to different types of alteration and fracture patterns show distinct changes in their physical properties. The seismic reflectors observed on the vertical seismic profile (VSP) experiment performed during Leg 111 may have been caused by low velocity zones resulting from alteration. The amount of fracturing and hydrothermal alteration in several zones also may have contributed to the acoustic impedance contrast necessary to produce the E5 reflector. Poisson's ratios calculated from laboratory velocity measurements show several low values at depths ranging from 1600 mbsf to 2000 mbsf, which tends to follow similar trends obtained from previous oceanic refraction experiments. A comparison of physical properties between samples recovered from Hole 504B and ophiolite studies in the Bay of Islands and Oman shows a good correlation with the Bay of Islands but significant differences from the measurements performed in the Oman complex.

Compressional and shear wave velocities and elastic constants at DSDP Leg 59 Holes

Prior to the Deep Sea Drilling Project the composition of the oceanic crust could only be inferred from seismic-refraction and gravity data and the recovery of a wide variety of dredged rocks. Through the success of the Deep Sea Drilling Project, it is now clear that the top of oceanic Layer 2 usually consists of basalt. Several laboratory studies (e.g., Fox et al., 1972; Christensen and Shaw, 1970; Hyndman and Drury, 1976) have demonstrated that the seismic velocities of oceanic basalt are similar to velocities reported from refraction studies of Layer 2 and that the variability in Layer 2 velocities has many causes, the most important being fracturing and sea-floor alteration produced by the interaction of basalt and sea water (Christensen and Salisbury, 1973). To date, most reported measurements of velocities in oceanic basalts are from samples obtained from the main ocean basins. With the exception of an earlier study of velocities and related elastic properties of a suite of rocks from DSDP Sites 292, 293, 294, and 296 located in the Philippine Sea (Christensen et al., 1975; Fountain et al., 1975), elastic properties have not been determined for oceanic rocks from marginal basins. In this chapter compressional- and shear-wave velocities and elastic constants are reported at elevated confining pressures for basalt and volcanic breccias from Holes 447A, 448, and 448A.

(Table 1) Compressional-wave and shear-wave velocities and elastic constants from DSDP Legs 69 and 70

Shear-wave and compressional-wave velocities of 26 basalt samples collected at Site 504 during Deep Sea Drilling Project Legs 69 and 70 were measured at elevated confining pressures. The young basalts have higher velocities than average DSDP basalts, because of their lack of alteration. Measurements of sample porosity are combined with laboratory and in situ velocity measurements to yield estimates of total crustal porosity: 13% at the top of Layer 2, and very low porosity below a depth of 2.0 km.

(Table 1) Compressional and shear wave velocities and elastic constants of DSDP Hole 83-504B basalts

Compressional and shear wave velocities at confining pressures to 6 kb, densities, and porosities were measured for 32 samples obtained from 836 to 1350 m below seafloor (BSF) in Hole 504B, the section drilled on Leg 83 of the Deep Sea Drilling Project. These data in combination with similar measurements on 28 basalt samples from the section from 274.5 to 836 m, drilled on Legs 69 and 70, provide a comprehensive set of physical property data for over 1000 m of oceanic crust. The velocities, densities, and porosities measured in the laboratory exhibit greater variability in the upper portion of the hole. In general, compressional and shear wave velocities and densities increase with depth, reaching average values at 1 kbar of Vp = 6.45 km/s, Ks = 3.45 km/s and p = 2.94 g/cm3 within the sheeted dike section. Porosities decrease with depth to values generally less than 1% near the bottom of the hole