Isomerization of the Newly Discovered Interstellar Molecule SiCN to SiNC Through Two Transition States

A range of highly correlated ab initio methods is used to predict the geometrical parameters of silicon cyanide (SiCN), silicon isocyanide (SiNC), and two transition states (2A’ and 2A’’) for the isomerization reaction transforming one to the other. Also predicted are dipole moments, rotational constants, and harmonic vibrational frequencies. At all levels of theory, the SiCN and SiNC molecules are predicted to have linear equilibrium structures. The SiNC isomer is found to lie 1.5 kcal/mol above the SiCN species at the coupled cluster (CC) with single, double, and full triple excitations (CCSDT) level of theory with the correlation-consistent polarized valence quadruple zeta (cc-pVQZ) basis set. These theoretical predictions complement the recent laboratory production of SiCN and SiNC and subsequent astronomical detection of SiCN in the envelope of the C Star IRC110216/CW Leo. The theoretical Be values of 5481 MHz (SiCN) and 6316 MHz (SiNC) at the CC with single, double, and iterative partial triple excitations (CCSDT-3) level of theory with the cc-pVQZ basis set are consistent with the experimental B0 values of 5543 MHz (SiCN) and 6397 MHz (SiNC). The transition states for the isomerization reaction SiCN-\u3eSiCN are found to proceed through the 2A’ and 2A’’ surfaces, which lie 20.9 and 21.8 kcal/mol above the SiCN minimum at the cc-pVQZ CCSDT-3 level of theory. The ground states of SiCN and SiNC radicals are subject to Renner–Teller interactions. At the CC with single, double, and perturbative triple excitations [CCSD(T)] level of theory, the Renner parameters and the averaged harmonic bending vibrational frequencies are determined to be 0.318 and 249 cm-1 for SiCN and 0.412 and 195 cm-1 for SiNC

Characterization of Singlet Ground and Low-Lying Electronic Excited States of Phosphaethyne and Isophosphaethyne

The singlet ground _X˜ 1_+_ and excited _1_− , 1__ states of HCP and HPC have been systematically investigated using ab initio molecular electronic structure theory. For the ground state, geometries of the two linear stationary points have been optimized and physical properties have been predicted utilizing restricted self-consistent field theory, coupled cluster theory with single and double excitations _CCSD_, CCSD with perturbative triple corrections _CCSD_T__, and CCSD with partial iterative triple excitations _CCSDT-3 and CC3_. Physical properties computed for the global minimum _X˜ 1_+HCP_ include harmonic vibrational frequencies with the cc-pV5Z CCSD_T_ method of _1=3344 cm−1, _2=689 cm−1, and _3=1298 cm−1. Linear HPC, a stationary point of Hessian index 2, is predicted to lie 75.2 kcal mol−1 above the global minimum HCP. The dissociation energy D0_HCP_X˜ 1_+_→H_2S_+CP_X 2_+__ of HCP is predicted to be 119.0 kcal mol−1, which is very close to the experimental lower limit of 119.1 kcal mol−1. Eight singlet excited states were examined and their physical properties were determined employing three equation-of-motion coupled cluster methods _EOM-CCSD, EOM-CCSDT-3, and EOM-CC3_. Four stationary points were located on the lowest-lying excited state potential energy surface, 1_− →1A_, with excitation energies Te of 101.4 kcal mol−1_1A_ HCP_, 104.6 kcal mol−1_1_− HCP_, 122.3 kcal mol−1_1A_ HPC_, and 171.6 kcal mol−1_1_− HPC_ at the cc-pVQZ EOM-CCSDT-3 level of theory. The physical properties of the 1A_ state with a predicted bond angle of 129.5° compare well with the experimentally reported first singlet state _A˜ 1A__. The excitation energy predicted for this excitation is T0=99.4 kcal mol−1_34 800 cm−1 , 4.31 eV_, in essentially perfect agreement with the experimental value of T0=99.3 kcal mol−1_34 746 cm−1 ,4.308 eV_. For the second lowest-lying excited singlet surface, 1_→1A_, four stationary points were found with Te values of 111.2 kcal mol−1 _21A_ HCP_, 112.4 kcal mol−1 _1_ HPC_, 125.6 kcal mol−1_2 1A_ HCP_, and 177.8 kcal mol−1_1_ HPC_. The predicted CP bond length and frequencies of the 2 1A_ state with a bond angle of 89.8° _1.707 Å, 666 and 979 cm−1_ compare reasonably well with those for the experimentally reported C ˜ 1A_ state _1.69 Å, 615 and 969 cm−1_. However, the excitation energy and bond angle do not agree well: theoretical values of 108.7 kcal mol−1 and 89.8° versus experimental values of 115.1 kcal mol−1 and 113°

Referrals for suspected hematologic malignancy: A survey of primary care physicians

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/91356/1/23172_ftp.pd

Final Report of the AFIT Quality Initiative Internal Discovery Committee

This document contains results of a study designed to document the key elements for student success at AFIT in our continuing education and graduate programs and discover to what degree they exist at AFIT. The effort represents an attempt to guide improvement of our graduate and continuing education programs through experience available from our faculty, staff and students. The process outlined herein was designed to achieve success by allowing the participants to define what it means to succeed and then self-assess the presence of these factors at AFIT. It’s therefore a true internal discovery process since its output reflects the state of our internal understanding of teaching and learning excellence. This inclusive approach, which garnered participation from 400 people across AFIT’s schools, will be used in conjunction with the external committee\u27s recommendations to determine a course of action to invest into AFIT\u27s instructional capabilities

Board of Regents

This report, fifteenth of an annual series, describes 1993 mineral, oil and gas, and geothermal activities and accomplishments in Nevada: production statistics, exploration and development including drilling for petroleum and geothermal resources, discoveries of orebodies, new mines opened, and expansion and other activities of existing mines. Statistics of known gold and silver deposits, and directories of mines and mills are included. For more information contact

Increased RPA1 gene dosage affects genomic stability potentially contributing to 17p13.3 duplication syndrome

A novel microduplication syndrome involving various-sized contiguous duplications in 17p13.3 has recently been described, suggesting that increased copy number of genes in 17p13.3, particularly PAFAH1B1, is associated with clinical features including facial dysmorphism, developmental delay, and autism spectrum disorder. We have previously shown that patient-derived cell lines from individuals with haploinsufficiency of RPA1, a gene within 17p13.3, exhibit an impaired ATR-dependent DNA damage response (DDR). Here, we show that cell lines from patients with duplications specifically incorporating RPA1 exhibit a different although characteristic spectrum of DDR defects including abnormal S phase distribution, attenuated DNA double strand break (DSB)-induced RAD51 chromatin retention, elevated genomic instability, and increased sensitivity to DNA damaging agents. Using controlled conditional over-expression of RPA1 in a human model cell system, we also see attenuated DSB-induced RAD51 chromatin retention. Furthermore, we find that transient over-expression of RPA1 can impact on homologous recombination (HR) pathways following DSB formation, favouring engagement in aberrant forms of recombination and repair. Our data identifies unanticipated defects in the DDR associated with duplications in 17p13.3 in humans involving modest RPA1 over-expression

The MOST view of Cepheids

The MOST space telescope observed four Cepheid variables so far, all of different subtypes. Here we summarize the results obtained and the possible ways to continue to study these stars

Chronic psychosocial and financial burden accelerates 5-year telomere shortening: findings from the Coronary Artery Risk Development in Young Adults Study.

Leukocyte telomere length, a marker of immune system function, is sensitive to exposures such as psychosocial stressors and health-maintaining behaviors. Past research has determined that stress experienced in adulthood is associated with shorter telomere length, but is limited to mostly cross-sectional reports. We test whether repeated reports of chronic psychosocial and financial burden is associated with telomere length change over a 5-year period (years 15 and 20) from 969 participants in the Coronary Artery Risk Development in Young Adults (CARDIA) Study, a longitudinal, population-based cohort, ages 18-30 at time of recruitment in 1985. We further examine whether multisystem resiliency, comprised of social connections, health-maintaining behaviors, and psychological resources, mitigates the effects of repeated burden on telomere attrition over 5 years. Our results indicate that adults with high chronic burden do not show decreased telomere length over the 5-year period. However, these effects do vary by level of resiliency, as regression results revealed a significant interaction between chronic burden and multisystem resiliency. For individuals with high repeated chronic burden and low multisystem resiliency (1 SD below the mean), there was a significant 5-year shortening in telomere length, whereas no significant relationships between chronic burden and attrition were evident for those at moderate and higher levels of resiliency. These effects apply similarly across the three components of resiliency. Results imply that interventions should focus on establishing strong social connections, psychological resources, and health-maintaining behaviors when attempting to ameliorate stress-related decline in telomere length among at-risk individuals

Synesthesia, transformation and synthesis : toward a multi-sensory pedagogy of the image

Peer reviewedPostprintPostprintPostprintPostprin