- Award ID(s):
- 2107923
- NSF-PAR ID:
- 10540338
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry A
- Volume:
- 128
- Issue:
- 37
- ISSN:
- 1089-5639
- Format(s):
- Medium: X Size: p. 7816-7829
- Size(s):
- p. 7816-7829
- Sponsoring Org:
- National Science Foundation
More Like this
-
The anionic products following (H + H + ) abstraction from o -, m -, and p -methylphenol (cresol) are investigated using flowing afterglow-selected ion flow tube (FA-SIFT) mass spectrometry and anion photoelectron spectroscopy (PES). The PES of the multiple anion isomers formed in this reaction are reported, including those for the most abundant isomers, o -, m - and p -methylenephenoxide distonic radical anions. The electron affinity (EA) of the ground triplet electronic state of neutral m -methylenephenoxyl diradical was measured to be 2.227 ± 0.008 eV. However, the ground singlet electronic states of o - and p -methylenephenoxyl were found to be significantly stabilized by their resonance forms as a substituted cyclohexadienone, resulting in measured EAs of 1.217 ± 0.012 and 1.096 ± 0.007 eV, respectively. Upon electron photodetachment, the resulting neutral molecules were shown to have Franck–Condon active ring distortion vibrational modes with measured frequencies of 570 ± 180 and 450 ± 80 cm −1 for the ortho and para isomers, respectively. Photodetachment to excited electronic states was also investigated for all isomers, where similar vibrational modes were found to be Franck–Condon active, and singlet–triplet splittings are reported. The thermochemistry of these molecules was investigated using FA-SIFT combined with the acid bracketing technique to yield values of 341.4 ± 4.3, 349.1 ± 3.0, and 341.4 ± 4.3 kcal mol −1 for the o -, m -, and p -methylenephenol radicals, respectively. Construction of a thermodynamic cycle allowed for an experimental determination of the bond dissociation energy of the O–H bond of m -methylenephenol radical to be 86 ± 4 kcal mol −1 , while this bond is significantly weaker for the ortho and para isomers at 55 ± 5 and 52 ± 5 kcal mol −1 , respectively. Additional EAs and vibrational frequencies are reported for several methylphenyloxyl diradical isomers, the negative ions of which are also formed by the reaction of cresol with O − .more » « less
-
more » « less
Abstract Spirotrichonymphea, one of the six classes of phylum Parabasalia, are characterized by bearing many flagella in spiral rows, and they occur exclusively in the guts of termites. Phylogenetic relationships among the 13 described genera are not well understood due to complex morphological evolution and a paucity of molecular data. One such understudied genus is
Spironympha . It has been variously considered a valid genus, a subgenus ofSpirotrichonympha , or an “immature” life cycle stage ofSpirotrichonympha . To clarify this, we sequenced the small subunit rRNA gene sequences ofSpironympha andSpirotrichonympha cells isolated from the hindguts ofReticulitermes species andHodotermopsis sjostedti and confirmed the molecular identity ofH. sjostedti symbionts using fluorescence in situ hybridization.Spironympha as currently circumscribed is polyphyletic, with bothH. sjostedti symbiont species branching separately from the “true”Spironympha fromReticulitermes . Similarly, theSpirotrichonympha symbiont ofH. sjostedti branches separately from the “true”Spirotrichonympha found inReticulitermes . Our data supportSpironympha fromReticulitermes as a valid genus most closely related toSpirotrichonympha , though its monophyly and interspecific relationships are not resolved in our molecular phylogenetic analysis. We propose three new genera to accommodate theH. sjostedti symbionts and two new species ofSpirotrichonympha fromReticulitermes . -
more » « less
SUMMARY The seismic quality factor (Q) of the Earth’s mantle is of great importance for the understanding of the physical and chemical properties that control mantle anelasticity. The radial structure of the Earth’s Q is less well resolved compared to its wave speed structure, and large discrepancies exist among global 1-D Q models. In this study, we build a global data set of amplitude measurements of S, SS, SSS and SSSS waves using earthquakes that occurred between 2009 and 2017 with moment magnitudes ranging from 6.5 to 8.0. Synthetic seismograms for those events are computed in a 1-D reference model PREM, and amplitude ratios between observed and synthetic seismograms are calculated in the frequency domain by spectra division, with measurement windows determined based on visual inspection of seismograms. We simulate wave propagation in a global velocity model S40RTS based on SPECFEM3D and show that the average amplitude ratio as a function of epicentral distance is not sensitive to 3-D focusing and defocusing for the source–receiver configuration of the data set. This data set includes about 5500 S and SS measurements that are not affected by mantle transition zone triplications (multiple ray paths), and those measurements are applied in linear inversions to obtain a preliminary 1-D Q model QMSI. This model reveals a high Q region in the uppermost lower mantle. While model QMSI improves the overall datafit of the entire data set, it does not fully explain SS amplitudes at short epicentral distances or the amplitudes of the SSS and SSSS waves. Using forward modelling, we modify the 1-D model QMSI iteratively to reduce the overall amplitude misfit of the entire data set. The final Q model QMSF requires a stronger and thicker high Q region at depths between 600 and 900 km. This anelastic structure indicates possible viscosity layering in the mid mantle.
