Infrared absorption of gaseous ClCS detected with time-resolved Fourier-transform spectroscopy.
A transient infrared absorption spectrum of gaseous ClCS was detected with a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. ClCS was produced upon irradiating a flowing mixture of Cl2CS and N2 or CO2 with a KrF excimer laser at 248 nm. A transient band in the region of 1160-1220 cm-1, which diminished on prolonged reaction, is assigned to the C-S stretching (nu1) mode of ClCS. Calculations with density-functional theory (B3P86 and B3LYP/aug-cc-pVTZ) predict the geometry, vibrational wave numbers, and rotational parameters of ClCS. The rotational contour of the spectrum of ClCS simulated based on predicted rotational parameters agrees satisfactorily with experimental observation; from spectral simulation, the band origin is determined to be at 1194.4 cm-1. Reaction kinetics involving ClCS, CS, and CS2 are discussed.
Infrared absorption of gaseous c-ClCOOH and t-ClCOOH recorded with a step-scan Fourier-transform spectrometer.
Two conformers of ClCOOH were produced upon irradiation at 355 nm of a gaseous flowing mixture of Cl(2), HCOOH, and N(2). A step-scan Fourier-transform infrared spectrometer coupled with a multipass absorption cell was utilized to monitor the transient spectra of ClCOOH. Absorption bands with origins at 1808.0 and 1328.5 cm(-1) are attributed to the C=O stretching and COH bending modes of t-ClCOOH, respectively; those at 1883.0 and 1284.9 cm(-1) are assigned as the C=O stretching and COH bending modes of c-ClCOOH, respectively. These observed vibrational wavenumbers agree with corresponding values for t-ClCOOH and c-ClCOOH predicted with B3LYP/aug-cc-pVTZ density-functional theory and the observed rotational contours agree satisfactorily with simulated bands based on predicted rotational parameters. The observed relative intensities indicate that t-ClCOOH is more stable than c-ClCOOH by approximately 3 kJ mol(-1). A simple kinetic model is employed to account for the production and decay of ClCOOH.
Palaeocarpinus (Extinct Betulaceae) from Northwestern China: New Evidence for Paleocene Floristic Continuity between Asia, North America, and Europe
Spiny-bracted fruits of Palaeocarpinus Crane, a genus of Betulaceae previously known only from Europe and North America, have been discovered in the Paleocene of Altai, northwestern China. The fruits are found in association with abundant Corylus-like foliage and staminate catkins containing Corylus-like pollen. Because of problems distinguishing leaves of Corylus from those of extinct betulaceous genera, we place these leaves in the genus Corylites Gardner ex Seward & Holttum. The fruits, staminate catkins, pollen, and leaves from Altai were probably all produced by a single species. Palaeocarpinus orientalis is nearly identical in its morphology to Palaeocarpinus joffrensis from the Paleocene of North America except in the more rounded primary bracts of the associated staminate catkins. The species is less similar to Palaeocarpinus laciniata from the Paleocene of southern England.