Features of Molecular Structure Beneficial for Optical Pumping

Fast and efficient state preparation of molecules can be accomplished by optical pumping. Molecular structure that most obviously facilitates cycling involves a strong electronic transition, with favorable vibrational branching (diagonal Franck-Condon factors, aka FCFs) and without any intervening electronic states. Here, we propose important adjustments to those criteria, based on our experience optically pumping SiO$^+$. Specifically, the preference for no intervening electronic states should be revised, and over-reliance on FCFs can miss important features. The intervening electronic state in SiO$^+$is actually found to be beneficial in ground rotational state preparation, by providing a pathway for population to undergo a parity flip. This contribution demonstrates the possibility that decay through intervening states may help state preparation of non-diagonal or polyatomic molecules. We also expand upon the definition of favorable branching. In SiO$^+$, we find that the off-diagonal FCFs fail to reflect the vibrational heating versus cooling rates. Since the branching rates are determined by transition dipole moments (TDMs) we introduce a simple model to approximate the TDMs for off-diagonal decays. We find that two terms, set primarily by the slope of the dipole moment function ($d\mu/dx$) and offset in equilibrium bond lengths ($\Delta x = r_e^g-r_e^e$), can add (subtract) to increase (decrease) the magnitude of a given TDM. Applying the model to SiO$^+$, we find there is a fortuitous cancellation, where decay leading to vibrational excitation is reduced, causing optical cycling to lead naturally to vibrational cooling

Time-resolved measurements of product formation in the low-temperature (550-675 K) oxidation of neopentane : a probe to investigate chain-branching mechanism

Product formation, in particular ketohydroperoxide formation and decomposition, were investigated in time-resolved, Cl-atom initiated neopentane oxidation experiments in the temperature range 550-675 K using a photoionization time-of-flight mass spectrometer. Ionization light was provided either by Advanced Light Source tunable synchrotron radiation or similar to 10.2 eV fixed energy radiation from a H-2-discharge lamp. Experiments were performed both at 1-2 atm pressure using a high-pressure reactor and also at similar to 9 Torr pressure employing a low-pressure reactor for comparison. Because of the highly symmetric structure of neopentane, ketohydroperoxide signal can be attributed to a 3-hydroperoxy-2,2-dimethylpropanal isomer, i.e. from a gamma-ketohydroperoxide (gamma-KHP). The photoionization spectra of the gamma-KHP measured at low-and high pressures and varying oxygen concentrations agree well with each other, further supporting they originate from the single isomer. Measurements performed in this work also suggest that the "Korcek" mechanism may play an important role in the decomposition of 3-hydroperoxy-2,2-dimethylpropanal, especially at lower temperatures. However, at higher temperatures where gamma-KHP decomposition to hydroxyl radical and oxy-radical dominates, oxidation of the oxy-radical yields a new important channel leading to acetone, carbon monoxide, and OH radical. Starting from the initial neopentyl + O-2 reaction, this channel releases altogether three OH radicals. A strongly temperature-dependent reaction product is observed at m/z = 100, likely attributable to 2,2-dimethylpropanedial.Peer reviewe

Products of Criegee intermediate reactions with NO2::experimental measurements and tropospheric implications

The reactions of Criegee intermediates with NO2 have been proposed as a potentially significant source of the important nighttime oxidant NO3, particularly in urban environments where concentrations of ozone, alkenes and NOx are high. However, previous efforts to characterize the yield of NO3 from these reactions have been inconclusive, with many studies failing to detect NO3. In the present work, the reactions of formaldehyde oxide (CH2OO) and acetaldehyde oxide (CH3CHOO) with NO2 are revisited to further explore the product formation over a pressure range of 4–40 Torr. NO3 is not observed; however, temporally resolved and [NO2]-dependent signal is observed at the mass of the Criegee–NO2 adduct for both formaldehyde- and acetaldehyde-oxide systems, and the structure of this adduct is explored through ab initio calculations. The atmospheric implications of the title reaction are investigated through global modelling.</p

Gene discovery in EST sequences from the wheat leaf rust fungus Puccinia triticina sexual spores, asexual spores and haustoria, compared to other rust and corn smut fungi

© 2011 Xu et al.; licensee BioMed Central Ltd. This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.DOI: 10.1186/1471-2164-12-161Background.Rust fungi are biotrophic basidiomycete plant pathogens that cause major diseases on plants and trees world-wide, affecting agriculture and forestry. Their biotrophic nature precludes many established molecular genetic manipulations and lines of research. The generation of genomic resources for these microbes is leading to novel insights into biology such as interactions with the hosts and guiding directions for breakthrough research in plant pathology. Results. To support gene discovery and gene model verification in the genome of the wheat leaf rust fungus, Puccinia triticina (Pt), we have generated Expressed Sequence Tags (ESTs) by sampling several life cycle stages. We focused on several spore stages and isolated haustorial structures from infected wheat, generating 17,684 ESTs. We produced sequences from both the sexual (pycniospores, aeciospores and teliospores) and asexual (germinated urediniospores) stages of the life cycle. From pycniospores and aeciospores, produced by infecting the alternate host, meadow rue (Thalictrum speciosissimum), 4,869 and 1,292 reads were generated, respectively. We generated 3,703 ESTs from teliospores produced on the senescent primary wheat host. Finally, we generated 6,817 reads from haustoria isolated from infected wheat as well as 1,003 sequences from germinated urediniospores. Along with 25,558 previously generated ESTs, we compiled a database of 13,328 non-redundant sequences (4,506 singlets and 8,822 contigs). Fungal genes were predicted using the EST version of the self-training GeneMarkS algorithm. To refine the EST database, we compared EST sequences by BLASTN to a set of 454 pyrosequencing-generated contigs and Sanger BAC-end sequences derived both from the Pt genome, and to ESTs and genome reads from wheat. A collection of 6,308 fungal genes was identified and compared to sequences of the cereal rusts, Puccinia graminis f. sp. tritici (Pgt) and stripe rust, P. striiformis f. sp. tritici (Pst), and poplar leaf rust Melampsora species, and the corn smut fungus, Ustilago maydis (Um). While extensive homologies were found, many genes appeared novel and species-specific; over 40% of genes did not match any known sequence in existing databases. Focusing on spore stages, direct comparison to Um identified potential functional homologs, possibly allowing heterologous functional analysis in that model fungus. Many potentially secreted protein genes were identified by similarity searches against genes and proteins of Pgt and Melampsora spp., revealing apparent orthologs. Conclusions. The current set of Pt unigenes contributes to gene discovery in this major cereal pathogen and will be invaluable for gene model verification in the genome sequence

SPECTROSCOPIC CHARATERIZATION OF ThF AND THE LOW-LYING STATES OF ThF+^+

Author Institution: Department of Chemistry, Emory University, Atlanta, GA 30322Theoretical calculations predict that internal electric fields as high as 90 GV/cm can be attained by polarizing the $^3\Delta_1$ state of ThF$^+$, 010502/1 (2008). \textit{"Prospects for an electron electric-dipole moment search in metastable ThO and ThF+"}} Consequently, this ion is of interest for investigation of the dipole moment of the electron. However, spectroscopic data have not been reported previously for ThF or ThF$^+$. We have used laser induced fluorescence and resonantly enhanced two-photon ionization to examine ThF. Multiple electronic transitions were observed in the 19530-21300 \wn range. Rotationally resolved data have been obtained, and the ground state is shown to be X$^2\Delta$_3_/_2. Pulsed field ionization - zero electron kinetic energy spectra have been recorded for the ThF+ cation. Vibronic progressions of the X$^1\Sigma^+$ and excited $^3\Delta$ states have been identified. The term energy for the $^3\Delta_1$ state was found to be T$_0$=330 \wn. Details of the experiments and spectroscopic constants for ThF and ThF$^+$ will be reported