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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Bioaccumulation of hydroxylated polychlorinated biphenyls and pentachlorophenol in the serum of northern elephant seal pups (Mirounga angustirostris)

Northern elephant seals (NES) (Mirounga angustirostris) from the Año Nuevo State Reserve (CA, USA) were sampled at 1-, 4-, 7- and 10-week post-weaning. Concentrations of hydroxylated polychlorinated biphenyls (HO-PCBs) and their parent PCBs were measured in the serum of each individual. The ΣHO-PCB concentrations in the serum increased significantly between early and late fast (from 282±20 to 529±31 pg/mL). This increase might result from a mobilisation of HO-PCBs transferred from the mother during gestation and/or lactation and stored in the pup's liver. Food deprivation has been shown to exacerbate biotransformation capacities in mammals, birds and fish. The HO-penta-CBs was the predominant homologue group, followed by HO-hexa-CBs and HO-hepta-CBs. No preferential pathway for the metabolism of HO-PCBs (HO-direct insertion or NIH-shift of a chlorine atom) could be evidenced. The concentrations of pentachlorophenol (PCP) in the serum of weaned NES increased from 103±7 pg/mL at early fast to 246±41 pg/mL at late fast, which is within the range of PCP concentrations usually encountered in marine mammals. - Highlights: • Σ HO-PCB concentrations in serum significantly increased between early and late fast. • The HO-penta-CBs were the predominant homologue group measured in serum. • No preferential pathway for the metabolism of HO-PCBs could be evidenced. • PCP concentrations in serum significantly increased between early and late fast.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Theoretical spectroscopy study of the low-lying electronic states of UX and UX{sup +}, X = F and Cl

Spectroscopic constants (T{sub e}, r{sub e}, B{sub 0}, ω{sub e}, and ω{sub e}x{sub e}) have been calculated for the low-lying electronic states of UF, UF{sup +}, UCl, and UCl{sup +} using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess Hamiltonians for the U atom. Spin orbit (SO) effects were included a posteriori using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component methods for U{sup +} and UF{sup +}. Complete basis set (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω = 9/2 ground states. The first excited state of UCl was calculated to be an Ω = 7/2 state at 78 cm{sup −1} as opposed to the same state at 435 cm{sup −1} in UF, and the other low-lying states of UCl showed a similar compression relative to UF. Likewise, UF{sup +} and UCl{sup +} both have Ω = 4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states was energetically closer together in UCl{sup +} than in UF{sup +}, ranging up to 776 cm{sup −1} in UF{sup +} and only 438 cm{sup −1} in UCl{sup +}. As in previous studies, the final PP-based SO-CASPT2 results for UF{sup +} and UF agree well with experiment and are expected to be predictive for UCl and UCl{sup +}, which are reported here for the first time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Statistical simulation of multiple Compton backscattering process

A number of laboratories are currently developing monochromatic sources of X-rays and gamma quanta based on the Compton backscattering (CBS) of laser photons by relativistic electrons. Modern technologies are capable of providing a concentration of electrons and photons in the interaction point such that each primary electron can emit several hard photons. In contrast to the well-known nonlinear CBS process, in which an initial electron “absorbs” a few laser photons and emits a single hard one, the above-mentioned process can be called a multiple CBS process and is characterized by a mean number of emitted photons. The present paper is devoted to simulating the parameters of a beam of back scattered quanta based on the Monte Carlo technique. It is shown that, even in the case of strong collimation of a resulting photon beam, the radiation monochromaticity may deteriorate because of the contribution coming from the multiple photon emission, which is something that must be considered while designing new CBS sources.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

Implementation of Distributed Memory Computing in MOSAIC to Enable Large 3D Simulations of Irradiated Concrete

The concrete biological shield (CBS) of light-water reactors protects workers and the surrounding environment by absorbing neutron and gamma irradiation emitted from the reactor core. The radiation dose increases with the CBS’s operational time and, in the long term, becomes significant enough to raise the question of irradiation effects on concrete—and particularly on the structural integrity of the CBS. Irradiation-induced damage has been identified as one of the main degradation mechanisms in the CBS. Neutron radiation causes the swelling of aggregate-forming minerals at different rates and amplitudes depending on the mineral’s nature. Silicate-bearing minerals such as quartz are particularly sensitive to neutron radiation and experience up to 17.8% volumetric expansion. Aggregates comprise several minerals with different orientations and are, therefore, subject to cracking as a result of mismatch strains. Additionally, the swelling of aggregates creates significant stresses in the surrounding cement paste matrix, which also results in crack formation. In parallel with the collection of characterization and irradiation test data, development of modeling and simulation tools for irradiated concrete is ongoing with the support of the US Department of Energy Office of Nuclear Energy’s Light Water Reactor Sustainability (LWRS) program. This effort resulted in the development and application of the fast-Fourier transform (FFT)–based code Microstructure-Oriented Scientific Analysis of Irradiated Concrete (MOSAIC) at Oak Ridge National Laboratory.

61 RADIATION PROTECTION AND DOSIMETRY↗
NASA NTRS1981

Endurance tests with large-bore tapered-roller bearings to 2.2 million DN

Endurance life tests were run with standard design and optimized high-speed design 120.65-mm-(4.750-in.-) bore tapered-roller bearings at shaft speeds of 12,500 and 18,500 rpm, respectively. Standard design bearings of vacuum melted AISI 4320 and CBS-1000M, and high-speed design bearings of CBS-1000M and through-hardened AISI M-50 were run under heavy combined radial and thrust load until fatigue failure or until a preset cutoff time of 1100 hours was reached. Standard design bearings made from CBS 1000M material ran to a 10 percent life approximately six times rated catalog life. Twelve identical bearings of AISI 4320 material ran to ten times rated catalog life without failure. Cracking and fracture of the cones of AISI M-50 high-speed design bearings occurred at 18,500 rpm due to high tensile hoop stresses. Four CBS 1000M high-speed design bearings ran to twenty-four times rated catalog life without any spalling, cracking or fracture failures.

Parker, R. J.↗
NASA NTRS1981

Endurance tests with large-bore tapered-roller bearings to 2.2 million DN

Endurance life tests were run with standard-design bearings of vacuum-melted AISI 4320 and CBS-1000M at 12,500 rpm, and high-speed bearings of CBS-1000M and trough-hardened AISI M-50 at 18,500 rpm. Both sets of bearings were of 120.65 mm bore-tapered roller type, and were run under heavy combined radial and thrust loads until either fatigue failure or a preset cutoff time of 1100 hours was reached. It was found that: (1) the CBS-1000M standard-design bearings ran to a 10% life approximately six times that of the rated catalog life; (2) twelve identical bearings of AISI 4320 ran to ten times rated catalog life without failure; (3) cracking and fracture of the cones of AISI M-50 high-speed design bearings occurred at 18,500 rpm due to high tensile hoop stresses; and (4) four CBS 1000M high-speed bearings ran to twenty-four times rated catalog life without spalling, cracking or fracture failures.

Parker, R. J.↗
NASA NTRS1999

TMI Rain Rate Estimation Over Land and Ocean Utilizing Convective and Stratiform Discrimination

Tropical Rainfall Measuring Mission (TRMM) Microwave Imager (TMI) radiometer brightness temperature data in the 85 GHz channel (T85) reveal distinct local minima in a regional map containing a Mesoscale Convective System (MCS). This is because of relatively small footprint size (approximately 5.5 km) and strong extinction properties in this channel of the TMI. A map of rain rate for that region, deduced from simultaneous measurements made by the Precipitation Radar (PR) on board the TRMM satellite, reveals that these T85 minima, produced by scattering, correspond to local PR rain maxima. Utilizing the PR rain rate map as a guide, we infer from TMI data the presence of three different kinds of thunderstorms or Cbs. They are young, mature, and decaying Cbs that have a scale of about 20 km on the average. Two parameters enable us to infer these three kinds of Cbs objectively: a) the magnitude of scattering depression deduced from local T85 minima and b) the mean horizontal gradient of T85 around such minima. Knowing the category of a given Cb, we can estimate the rain rate associated with it. Such estimation is done with the help of relationships linking T85 minimum to rain rate in each Cb type. Similarly, a weak background rain rate in all the areas where T85 is less than 260 K is deduced with another relationship linking T85 to rain rate. In our rain retrieval model, this background rain constitutes the stratiform rain where the Cbs are absent. Initially, these relationships are optimized or tuned utilizing the PR and TMI data of a few MCS events. After such tuning, the model is applied to independent MCS cases. The areal distribution of light (1-10 mm/hr), moderate (10-20 mm/hr), and intense (> 20 mm/hr) rain rates are retrieved satisfactorally. Accuracy in the estimates of the light, moderate and intense rain areas and the mean rain rates associated with such areas in these independent MCS cases is on the average about 15%. Taking advantage of this ability of our retrieval method, one could derive the latent heat input into the atmosphere over the 760 km wide swath of the TMI radiometer in the tropics.

Prabhakara, C.↗
NASA NTRS1999

A TRMM Microwave Radiometer Rain Rate Estimation Method with Convective and Stratiform Discrimination

Tropical Rainfall Measuring Mission (TRMM) Microwave Imager (TMI) radiometer brightness temperature data in the 85 GHz channel (T85) reveal distinct local minima (T85min) in a regional map containing a Mesoscale Convective System (MCS). This is because of relatively small footprint size (approximately 5.5 km) and strong extinction properties in this channel of the TMI. A map of surface rain rate for that region, deduced from simultaneous measurements made by the Precipitation Radar (PR) on board the TRMM satellite, reveals that these T85(sub min), produced by scattering, correspond to local PR rain maxima. Utilizing the PR rain rate map as a guide, we infer empirically from TMI data the presence of three different kinds of thunderstorms or Cbs. These Cbs are classified as young, mature, and decaying types, and are assumed to have a scale of about 20 km on the average. Two parameters are used to classify these three kinds of Cbs based on the T85 data: a) the magnitude of scattering depression deduced from local T85(sub min) and b) the mean horizontal gradient of T85 around such minima. Knowing the category of a given Cb, we can estimate the rain rate associated with it. Such estimation is done with the help of relationships linking T85min to rain rate in each Cb type. Similarly, a weak background rain rate in all the areas where T85 is less than 260 K is deduced with another relationship linking T85 to rain rate. In our rain retrieval model, this background rain constitutes stratiform rain where the Cbs are absent. Initially, these relationships are optimized or tuned utilizing the PR and TMI data of a few MCS events. After such tuning, the model is applied to independent MCS cases. The areal distribution of light (1-10 mm/hr), moderate (10-20 mm/hr), and intense (>= 20 mm/hr) rain rates are retrieved satisfactorily. Accuracy in the estimates of the light, moderate, and intense rain areas and the mean rain rates associated with such areas in these independent MCS cases is on the average about 15 %. Taking advantage of this ability of our retrieval method, one could derive the latent heat input into the atmosphere over the 760 km wide swath of the TMI radiometer in the tropics.

Prabhakara, C.↗
NASA NTRS2021

The Current State and Future of the Former Central Nervous System Risk Managed by Space Radiation Element Part of NASA’s Human Research Program

Historically, the Space Radiation Element, as part of the NASA Human Research Program, was responsible for the scientific strategy and funding of research focused on characterizing and mitigating the effects of space radiation exposure on the central nervous system (CNS). During the past few of years, there have been two major changes that have affected the management of the science associated with the CNS risk. The first major change was the integration of several related risks: CNS (C), Behavioral medicine (B), and sensorimotor (S) to be managed as an integrated effort called CBS. CBS was formed to accelerate research on combined spaceflight stressors, specifically space radiation, microgravity, isolation, and confinement. CBS was managed by Human Factors and Behavioral Performance (HFBP) with support and inputs from Space Radiation as well as Human Health Countermeasures. Secondly, and more recently, the CNS risk was absorbed by the behavioral medicine risk currently also held by HFPB. As a result, the gaps associated with CNS were removed and aspects of them are represented in the BMED gaps (link). However, due to recent changes in element leadership, budget, and timeline, extensive restructuring of CBS is in progress. In addition, in an effort to harmonize datasets to be used in modelling efforts, an Animal Standardization TIM was held in June 2021 to standardize the type of behavioral and cognitive tasks as well as experimental set-ups. This presentation is an effort to communicate with the radiation research community concerning the strategy, management, and future of the former central nervous system risk and the role of the Space Radiation Element.

central nervous system↗
NASA NTRSDate not supplied

The Current State and Future of the Former Central Nervous System Risk Managed by Space Radiation Element Part of NASA’s Human Research Program

Historically, the Space Radiation Element, as part of the NASA Human Research Program, was responsible for the scientific strategy and funding of research focused on characterizing and mitigating the effects of space radiation exposure on the central nervous system (CNS). During the past few years, there have been two major changes that have affected the management of the science associated with the CNS risk. The first major change was the integration of several related risks: CNS (C), behavioral medicine (B), and sensorimotor (S) to be managed as an integrated effort called CBS. CBS was formed to accelerate research on combined spaceflight stressors, specifically space radiation, microgravity, isolation, and confinement. CBS was managed by Human Factors and Behavioral Performance (HFBP) with support and inputs from Space Radiation as well as Human Health Countermeasures. Secondly, and more recently, the CNS risk was absorbed by the behavioral medicine risk currently also held by HFPB. As a result, the gaps associated with CNS were removed and aspects of them are represented in the BMED gaps (link). However, due to recent changes in element leadership, budget, and timeline, extensive restructuring of CBS is in progress. In addition, in an effort to harmonize datasets to be used in modeling efforts, an Animal Standardization TIM was held in June 2021 to standardize the type of behavioral and cognitive tasks as well as experimental set-ups used in animal models of future funded research. This presentation is an effort to communicate with the radiation research community concerning the strategy, management, and future of the former central nervous system risk and the role of the Space Radiation Element.

Janice A Zawaski↗
DOE OSTI2015

Endogenous S-sulfhydration of PTEN helps protect against modification by nitric oxide

Highlights: • PTEN is S-sulfhydrated endogenously in SH-SY5Y human neuroblastoma cells. • Preventing this modification by knocking down CBS renders PTEN sensitive to NO. • pAkt levels are increased significantly in CBS siRNA-transfected cells. • H{sub 2}S functions as an endogenous regulator of PTEN in neuronal cells. - Abstract: Hydrogen sulfide (H{sub 2}S) is a gaseous regulatory factor produced by several enzymes, and plays a pivotal role in processes such as proliferation or vasodilation. Recent reports demonstrated the physiological and pathophysiological functions of H{sub 2}S in neurons. PTEN is a target of nitric oxide (NO) or hydrogen peroxide, and the oxidative modification of cysteine (Cys) residue(s) attenuates its enzymatic activity. In the present study, we assessed the effect of H{sub 2}S on the direct modification of PTEN and the resulting downstream signaling. A modified biotin switch assay in SH-SY5Y human neuroblastoma cells revealed that PTEN is S-sulfhydrated endogenously. Subsequently, site-directed mutagenesis demonstrated that both Cys71 and Cys124 in PTEN are targets for S-sulfhydration. Further, the knockdown of cystathionine β-synthetase (CBS) using siRNA decreased this modification in a manner that was correlated to amount of H{sub 2}S. PTEN was more sensitive to NO under these conditions. These results suggest that the endogenous S-sulfhydration of PTEN via CBS/H{sub 2}S plays a role in preventing the S-nitrosylation that would inhibition its enzymatic activity under physiological conditions.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Cystathionine gamma lyase-H2S contributes to osteoclastogenesis during bone remodeling induced by mechanical loading

Highlights: • This study investigated the role of H{sub 2}S and osteoclastogenesis in bone remodeling induced by mechanical loading in mice. • CSE-H{sub 2}S was a dominant H{sub 2}S generating system in osteoclasts, while CBS did not generate H{sub 2}S. • In CSE-deficient mice, osteoclastogenesis and tooth movement were inhibited, which could be rescued by a H{sub 2}S donor. Hydrogen sulfide (H{sub 2}S), a gaseous signaling molecule produced by cystathionine γ-lyase (CSE) and cystathionine β-synthase (CBS), influences bone remodeling in many ways. Osteoclasts play an important role in bone remodeling during tooth movement induced by mechanical loading, which increases the rate of tooth movement. Recently, we found that osteoclasts could produce H{sub 2}S. However, whether H{sub 2}S modulates bone remodeling by affecting osteoclasts remains unclear. In this study, we found that CSE-H{sub 2}S was a dominant H{sub 2}S generating system in osteoclasts, while CBS did not generate H{sub 2}S. A significant increase in CSE mRNA expression and H{sub 2}S production was observed in periodontal ligament (PDL) tissues of wild-type (WT) mice after 3 days of mechanical loading. CSE gene knockout led to a significant reduction in the number of maxillary osteoclasts and in the amount of tooth movement. The number of RANKL-induced TRAP-positive osteoclasts and the mRNA expression of osteoclast markers were downregulated after 6 days of incubation in monocytes extracted from CSE{sup −/−} mice. The expression of IL-1, IL-6 and TNF-α, which can stimulate osteoclastogenesis in periodontal tissue and serum samples, was lower in CSE{sup −/−} mice after mechanical loading. Application of the H{sub 2}S donor GYY4137 increased the number of RANKL-induced osteoclasts, the number of osteoclasts in periodontal tissues and tooth movement distance in CSE{sup −/−} mice. The results suggested that endogenous H{sub 2}S and CSE play vital roles in the osteoclastogenesis and alveolar bone resorption induced by mechanical loading.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

Chemoradiation With Concomitant Boosts Followed by Radical Surgery in Locally Advanced Cervical Cancer: Long-term Results of the ROMA-2 Prospective Phase 2 Study

Purpose: This prospective, phase 2 study aimed at assessing the efficacy of accelerated fractionation radiation therapy by concomitant boosts (CBs) associated with chemoradiation therapy (CRT) of the whole pelvis, in improving the rate of pathological complete response (pCR) to treatment in patients with International Federation of Gynaecology and Obstetrics (FIGO) stage IB2-IVA locally advanced cervical cancer. Methods and Materials: Neoadjuvant CRT included conformal irradiation of the whole pelvis with a total dose of 39.6 Gy (1.8 cGy/fraction, 22 fractions), plus additional irradiation of primary tumor and parametria with 10.8 Gy administered with CBs (0.9 cGy/fraction, 12 fractions, every other day). Concomitant chemotherapy included cisplatin (20 mg/m{sup 2}, days 1-4 and 26-30 of treatment), and capecitabine (1300 mg/m{sup 2}/daily, orally) during the first 2 and the last 2 weeks of treatment. Radical hysterectomy plus pelvic with or without aortic lymphadenectomy was performed within 6 to 8 weeks from CRT. Toxicity was recorded according to Radiation Therapy Oncology Group toxicity criteria and Chassagne grading system. Based on the Simon design, 103 cases were required, and the regimen would be considered active if >45 pCR were registered (α error = 0.05; β error = 0.1). Results: pCR was documented in 51 cases (50.5%), and the regimen was considered active, according to the planned statistical assumptions. At median follow-up of 36 months (range: 7-85 months), the 3-year local failure rate was 7%, whereas the 3-year disease-free and overall survival rates were 73.0% and 86.1%, respectively. Grade 3 leukopenia and neutropenia were reported in only 1 and 2 cases, respectively. Gastrointestinal toxicity was always grade 1 or 2. Conclusions: Addition of CBs in the accelerated fractionation modality to the whole pelvis chemoradiation followed by radical surgery results in a high rate of pathologically assessed complete response to CRT and a very encouraging local control rate, with acceptable toxicity.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2015

Structural effects of radiation-induced volumetric expansion on unreinforced concrete biological shields

Limited literature (Pomaro et al., 2011, Mirhosseini et al., 2014, Salomoni et al., 2014 and Andreev and Kapliy, 2014) is available on the structural analysis of irradiated concrete biological shield (CBS), although extended operations of nuclear powers plants may lead to critical neutron exposure above 1.0 × 10 +19 n cm ₋2 . To the notable exception of Andreev and Kapliy, available structural models do not account for radiation-induced volumetric expansion, although it was found to develop important linear dimensional change of the order of 1%, and, can lead to significant concrete damage (Le Pape et al., 2015). A 1D-cylindrical model of an unreinforced CBS accounting for temperature and irradiation effects is developed. Irradiated concrete properties are characterized probabilistically using the updated database collected by Oak Ridge National Laboratory (Field et al., 2015). The overstressed concrete ratio (OCR) of the CBS, i.e., the proportion of the wall thickness being subject to stresses beyond the resistance of concrete, is derived by deterministic and probabilistic analysis assuming that irradiated concrete behaves as an elastic materials. In the bi-axial compressive zone near the reactor cavity, the OCR is limited to 5.7%, i.e., 8.6 cm (3$_2^1$ in.), whereas, in the tension zone, the OCR extends to 72%, i.e., 1.08 m (42$_2^1$ in.). Finally, we find that these results, valid for a maximum neutron fluence on the concrete surface of 3.1 × 10 +19 n cm ₋2 (E > 0.1 MeV) and, obtained after 80 years of operation, give an indication of the potential detrimental effects of prolonged irradiation of concrete in nuclear power plants.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2021

A Massively Parallel Implementation of the CCSD(T) Method Using the Resolution-of-the-Identity Approximation and a Hybrid Distributed/Shared Memory Parallelization Model

In this work, a parallel algorithm is described for the coupled-cluster singles and doubles method augmented with a perturbative correction for triple excitations [CCSD(T)] using the resolution-of-the-identity (RI) approximation for two-electron repulsion integrals (ERIs). The algorithm bypasses the storage of four-center ERIs by adopting an integral-direct strategy. The CCSD amplitude equations are given in a compact quasi-linear form by factorizing them in terms of amplitude-dressed three-center intermediates. A hybrid MPI/OpenMP parallelization scheme is employed, which uses the OpenMP-based shared memory model for intranode parallelization and the MPI-based distributed memory model for internode parallelization. Parallel efficiency has been optimized for all terms in the CCSD amplitude equations. Two different algorithms have been implemented for the rate-limiting terms in the CCSD amplitude equations that entail and -scaling computational costs, where N O and N V denote the number of correlated occupied and virtual orbitals, respectively. One of the algorithms assembles the four-center ERIs requiring N V 4 and N O 2 N V 2 -scaling memory costs in a distributed manner on a number of MPI ranks, while the other algorithm completely bypasses the assembling of quartic memory-scaling ERIs and thus largely reduces the memory demand. It is demonstrated that the former memory-expensive algorithm is faster on a few hundred cores, while the latter memory-economic algorithm shows a better strong scaling in the limit of a few thousand cores. The program is shown to exhibit a near-linear scaling, in particular for the compute-intensive triples correction step, on up to 8000 cores. The performance of the program is demonstrated via calculations involving molecules with 24–51 atoms and up to 1624 atomic basis functions. As the first application, the complete basis set (CBS) limit for the interaction energy of the π-stacked uracil dimer from the S66 data set has been investigated. This work reports the first calculation of the interaction energy at the CCSD(T)/aug-cc-pVQZ level without local orbital approximation. The CBS limit for the CCSD correlation contribution to the interaction energy was found to be -8.01 kcal/mol, which agrees very well with the value -7.99 kcal/mol reported by Schmitz, Hättig, and Tew [ Phys. Chem. Chem. Phys. 2014 , 16 , 22167-22178]. The CBS limit for the total interaction energy was estimated to be -9.64 kcal/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Complementary Semiconducting Polymer Blends: The Influence of Conjugation-Break Spacer Length in Matrix Polymers

The concept of complementary semiconducting polymer blends ( c -SPBs) for efficient charge transport was recently proposed and established by our group. In this study, we aim to reveal the influence of the length of conjugation-break spacers (CBSs) on charge transport properties of the matrix polymers and their corresponding complementary polymer blends. A series of 11 DPP-based semiconducting polymers DPP-C m ( m = 2–12) that incorporate CBSs of 2–12 methylene units along the polymer backbones were prepared and characterized. The UV–vis spectra and the ultraviolet photoelectron spectroscopy (UPS) measurements show that the CBS length has marginal influence on the polymer absorption spectra, energy levels, and band gaps. It also has little impact on polymer decomposition temperatures. However, the CBS length has a profound influence on polymer phase transition and the heat of fusion. As for the melt transitions, an odd–even effect is observed from DPP-C2 to DPP-C7, in which polymers with even-numbered CBSs show higher melting points than their adjacent odd-numbered derivatives. We note the trend is opposite for heat of fusion. The polymers with odd-numbered CBSs exhibit larger heat of fusion, indicating higher ordering and crystallinity. The odd–even effect is also found in surface morphologies of the polymers by atomic force microscopy (AFM). The polymers with the even CBSs have a more interconnected feature that appear more fibrillar than the polymers with the odd linkages. As far as charge carrier mobility is concerned, the average number drops from 0.023 cm 2 V –1 s –1 to 7.9 × 10 –6 cm 2 V –1 s –1 as the CBS moves from C2 to C12. It is intriguing to observe that even-numbered polymers outperform the adjacent odd-numbered polymers, despite the fact that the latter show higher ordering and crystallinity in thin films. When these polymers are mixed with fully conjugated DPP-C0 (2 wt %, designated as tie chain polymer), the obtained c -SPBs witness a dramatic increase (2–4 orders of magnitude) in charge carrier mobility. Interestingly, the odd–even effect is not found for charge transport in the c -SPBs. This work reveals that the length of CBSs plays a significant role in charge transport properties of the matrix polymers and reconfirms that efficient charge transport properties of the c -SPB result from the interactions between matrix polymers and tie chain polymers. This begins to provide guidelines as to what spacer lengths may be utilized to offer the best balance between processing and charge transport properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Basis set convergence of the binding energies of strongly hydrogen-bonded atmospheric clusters

We investigate the basis set convergence of second order Møller Plesset perturbation theory for the binding energies of 11 strongly hydrogen-bonded clusters relevant to the atmosphere. The binding energies are calculated both as the uncorrected (UC) value, as well as by employing the counterpoise (CP) and the Same Number Of Optimized Parameters (SNOOP) correction schemes, with and without explicit correlation (F12). We find that the use of the F12 corrections is of utter importance for obtaining converged binding energies. Without F12 corrections at least a quadruple-ζ basis set is generally required to yield errors below 1 kcal mol -1 compared to the complete basis set (CBS) limit. Using coupled cluster methods we obtain a best estimate of the CCSD(T) CBS limit of the binding energies of the considered clusters and compare it with approximate DLPNO-CCSD(T) and DFT methods. We identify a pragmatic approach, relying solely on a series of double-ζ basis set calculations, for obtaining results in remarkably good agreement with our CBS estimate.

Chemistry↗
DOE OSTI2015

On the validity of the basis set superposition error and complete basis set limit extrapolations for the binding energy of the formic acid dimer

We report the variation of the binding energy of the Formic Acid Dimer with the size of the basis set at the Coupled Cluster with iterative Singles, Doubles and perturbatively connected Triple replacements [CCSD(T)] level of theory, estimate the Complete Basis Set (CBS) limit, and examine the validity of the Basis Set Superposition Error (BSSE)-correction for this quantity that was previously challenged by Kalescky, Kraka, and Cremer (KKC) [J. Chem. Phys. 140, 084315 (2014)]. Our results indicate that the BSSE correction, including terms that account for the substantial geometry change of the monomers due to the formation of two strong hydrogen bonds in the dimer, is indeed valid for obtaining accurate estimates for the binding energy of this system as it exhibits the expected decrease with increasing basis set size. We attribute the discrepancy between our current results and those of KKC to their use of a valence basis set in conjunction with the correlation of all electrons (i.e., including the 1s of C and O). We further show that the use of a core-valence set in conjunction with all electron correlation converges faster to the CBS limit as the BSSE correction is less than half than the valence electron/valence basis set case. The uncorrected and BSSE-corrected binding energies were found to produce the same (within 0.1 kcal/mol) CBS limits. We obtain CCSD(T)/CBS best estimates for D{sub e} = − 16.1 ± 0.1 kcal/mol and for D{sub 0} = − 14.3 ± 0.1 kcal/mol, the later in excellent agreement with the experimental value of −14.22 ± 0.12 kcal/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗