Towards multireference equivalents of the G2 and G3 methods

The effect of replacing the standard single-determinant reference wave functions in variants of G2 and G3 theory by multireference (MR) wave functions based on a full-valence complete active space has been investigated. Twelve methods of this type have been introduced and comparisons, based on a slightly reduced G2-1 test set, are made both internally and with the equivalent single-reference methods. We use CASPT2 as the standard MR-MP2 method and MRCl+Q as the higher correlation procedure in these calculations. We find that MR-G2(MP2,SVP), MR-G2(MP2), and MR-G3(MP2) perform comparably with their single-reference analogs, G2(MP2,SVP), G2(MP2), and G3(MP2), with mean absolute deviations (MADs) from the experimental data of 1.41, 1.54, and 1.23 kcal mol−1, compared with 1.60, 1.59, and 1.19 kcal mol−1, respectively. The additivity assumptions in the MR-Gn methods have been tested by carrying out MR-G2/MRCI+Q and MR-G3/MRCI+Q calculations, which correspond to large-basis-set MRCI+Q+ZPVE+HLC calculations. These give MADs of 1.84 and 1.58 kcal mol−1, respectively, i.e., the agreement with experiment is somewhat worse than that obtained with the MR-G2(MP2) and MR-G3(MP2) methods. In a third series of calculations, we have examined pure MP2 and MR-MP2 analogs of the G2 and G3 procedures by carrying out large-basis-set MP2 and CASPT2(+ZPVE+HLC) calculations. The resultant methods, which we denote G2/MP2, G3/MP2, MR-G2/MP2, and MR-G3/MP2, give MADs of 4.19, 3.36, 2.01, and 1.66 kcal mol−1, respectively. Finally, we have examined the effect of using MCQDPT2 in place of CASPT2 in five of our MR-Gn procedures, and find that there is a small but consistent deterioration in performance. Our calculations suggest that the MR-G3(MP2) and MR-G3/MP2 procedures may be useful in situations where a multireference approach is desirable.The authors would also like to thank the National Science Foundation International Division for providing travel funds to ~M.S.G. and M.A.F.! and the National Science Foundation Chemistry Division for supporting the research

The effects of symmetry and rigidity on non-adiabatic dynamics in tertiary amines:a time-resolved photoelectron velocity-map imaging study of the cage-amine ABCO

The non-adiabatic relaxation dynamics of the tertiary cage-amine azabicyclo[2.2.2]octane (ABCO, also known as quinuclidine) have been investigated following 3p Rydberg excitation at 201 nm using femtosecond time-resolved photoelectron imaging (TRPEI). The aim of the study was to investigate the influence of the rigid and symmetric cage structure found in ABCO on the general non-adiabatic relaxation processes commonly seen in other tertiary aliphatic amines (TAAs). Our data is compared with TRPEI results very recently obtained for several structurally less rigid TAA systems [J. O. F. Thompson et al., Chem. Sci., 2016, 7, 1826–1839] and helps to confirm many of the previously reported findings. The experimental results for ABCO in the short-time (<1 ps) regime strongly support earlier conclusions suggesting that planarization about the N-atom is not a prerequisite for efficient 3p–3s internal conversion. Additionally, individual photoelectron peaks within our ABCO data show no temporal shifts in energy. As confirmed by our supporting quantum mechanical calculations, this demonstrates that neither internal conversion within the 3p manifold or significant conformational re-organization are possible in the ABCO system. This result therefore lends strong additional support to the active presence of such dynamical effects in other, less conformationally restricted TAA species, where photoelectron peak shifts are commonly observed. Finally, the extremely long (>1 ns) 3s Rydberg state lifetime seen in ABCO (relative to other TAA systems at similar excitation energies) serves to illustrate the large influence of symmetry and conformational rigidity on intramolecular vibrational redistribution processes previously implicated in mediating this aspect of the overall relaxation dynamics

Chemical Characterization and Source Identification of Beached Oil from Two Areas Along the North-Western Coast of Qatar

Over the years there have been several reports of oil spills affecting particularly the northern coast of Qatar. In most cases, the source of oil spills is not identified. The spilled oils are very resistant to degradation and can affect the coastal ecosystem over many years. Even today, after 24 years, some of the oil that was spilled during the 1991 Gulf War can be found in sand, close to the Al Zubahra UNESCO site. The Maersk Oil Research and Technology Center in Doha (MO-RTC) has established the Oil Fingerprint project in collaboration with the University of Qatar and the University of Copenhagen. One of the objectives of the collaboration is to identify the potential source and origin of oil spills based on their chemical composition. A total of 38 samples were collected. During the sampling campaign it was discovered that the coast was contaminated with highly weathered oil that could originate from the Gulf War era but also with more fresh oil that most likely originates from recent oil spills in the Arabian Gulf. We therefore collected polluted soil samples and contaminated sediments from two main areas along the beach in North-western Qatar. The samples were analysed using gas chromatography - mass spectrometry in selected ion monitoring mode (GC-MS/SIM) and the oil composition was characterized. The likely source of the beached oil was identified by a comparison of diagnostic source ratios by comparing petroleum hydrocarbon fingerprints of steranes and hopanes of the spills against an oil database. The initial chemical fingerprinting based on selected ion chromatograms (SICs) of steranes (m/z 217) and hopanes (m/z 191), were remarkable similar as were the C29-/C30-Hopane ratios between sampling sites. However, a more detailed pixel-based analysis showed significant differences between samples. The process also included an assessment of the physical and biological weathering effects on the oil spills. Petroleum biomarker patterns (steranes and hopanes) are identical for all 14 samples included in this pilot study. The only differences observed were in the relative concentration of LMW and HMW steranes. This could be due to real source oil differences, however, the general weathering patterns indicate that these differences are more likely due to extensive weathering of especially two samples (9-02, 3-02) but also 8-01 and 10-01 shows severe weathering effects. Analysis of alkyl-PAHs provided an overall evaporative weathering degree for the samples. Distinct differences in the isomer patterns were observed for 3- to 4-ring alkyl-PAHs and this cannot be immediately explained as biodegradation. The largest fraction of the samples seems to originate from the same source but other sources are clearly present. A more detailed analysis with normalization to Euclidean norms within six selected SICs revealed more source specific information. In conclusion, the results indicate at least 2-3 different sources on the basis of differences in PAH isomer patterns. This was confirmed by visual inspection of SICs of C1-C3 alkyl-substituted phenanthrene, dibenzothophene, chrysene and pyrene isomers. Apart from the finding that the spills originate from several sources, the evaporation profiles indicated that not all of the spills are crude oils but that some are also heavy fuels. This suggests ongoing bunker flush off the coast of Qatar. These findings are of importance in further bioremediation processes in which, different approaches should be investigated to achieve high efficiency strategies if removal of oil pollutants from AlZubaraa area.qscienc

Long-term patient-important outcomes after septic shock : A protocol for 1-year follow-up of the CLASSIC trial

BackgroundIn patients with septic shock, mortality is high, and survivors experience long-term physical, mental and social impairments. The ongoing Conservative vs Liberal Approach to fluid therapy of Septic Shock in Intensive Care (CLASSIC) trial assesses the benefits and harms of a restrictive vs standard-care intravenous (IV) fluid therapy. The hypothesis is that IV fluid restriction improves patient-important long-term outcomes. AimTo assess the predefined patient-important long-term outcomes in patients randomised into the CLASSIC trial. MethodsIn this pre-planned follow-up study of the CLASSIC trial, we will assess all-cause mortality, health-related quality of life (HRQoL) and cognitive function 1 year after randomisation in the two intervention groups. The 1-year mortality will be collected from electronic patient records or central national registries in most participating countries. We will contact survivors and assess EuroQol 5-Dimension, -5-Level (EQ-5D-5L) and EuroQol-Visual Analogue Scale and Montreal Cognitive Assessment 5-minute protocol score. We will analyse mortality by logistic regression and use general linear models to assess HRQoL and cognitive function. DiscussionWith this pre-planned follow-up study of the CLASSIC trial, we will provide patient-important data on long-term survival, HRQoL and cognitive function of restrictive vs standard-care IV fluid therapy in patients with septic shock.Peer reviewe

Conservative vs liberal fluid therapy in septic shock (CLASSIC) trial-Protocol and statistical analysis plan

Introduction Intravenous (IV) fluid is a key intervention in the management of septic shock. The benefits and harms of lower versus higher fluid volumes are unknown and thus clinical equipoise exists. We describe the protocol and detailed statistical analysis plan for the conservative versus liberal approach to fluid therapy of septic shock in the Intensive Care (CLASSIC) trial. The aim of the CLASSIC trial is to assess benefits and harms of IV fluid restriction versus standard care in adult intensive care unit (ICU) patients with septic shock. Methods CLASSIC trial is an investigator-initiated, international, randomised, stratified, and analyst-blinded trial. We will allocate 1554 adult patients with septic shock, who are planned to be or are admitted to an ICU, to IV fluid restriction versus standard care. The primary outcome is mortality at day 90. Secondary outcomes are serious adverse events (SAEs), serious adverse reactions (SARs), days alive at day 90 without life support, days alive and out of the hospital at day 90 and mortality, health-related quality of life (HRQoL), and cognitive function at 1 year. We will conduct the statistical analyses according to a pre-defined statistical analysis plan, including three interim analyses. For the primary analysis, we will use logistic regression adjusted for the stratification variables comparing the two interventions in the intention-to-treat (ITT) population. Discussion The CLASSIC trial results will provide important evidence to guide clinicians' choice regarding the IV fluid therapy in adults with septic shock.Peer reviewe

Exchange of Cl+ between lone-pair donors and p-donors: a computational study

The chemistry of mono-adducts ([Cl-X]+) between Cl+ and a Lewis base (X = NH3, H2O, HF, PH3, H2S or HCl) has been investigated using ab initio molecular orbital calculations at the G2 level. The reactions of such mono-adducts with additional Lewis bases (Y) are found to give [Y-Cl]+ plus X, generally without an intermediate barrier, via a bis-adduct [Y-Cl-X]+. The binding energies of the bis-adduct and the reaction energies are related to the donor properties of the Lewis bases. The reactions between the mono-adducts [Cl-X]+ and the π-donors ethylene and acetylene yield chloriranium and chlorirenium ions, respectively. These reactions proceed via complexes that resemble either the reactants or products depending on the sign of the reaction energy, the latter in turn being determined by the donor ability of the Lewis base. Results for the chlorine systems are compared with those for the corresponding phosphorus systems investigated previously

Water Oil Emulsions Studied by Vibrational Sum Frequency Generation

Interfacial interactions between water and oil phases are present in various fields, in which other additives, such as surfactants, are utilized to minimize the surface stress between these phases to form an emulsion. However, the consequence of adding additives is not always easy to understand or to control, due to the plethora of parameters that control the production of an emulsion phase. There are several macroscopic techniques to study the properties of emulsions. Nevertheless, these techniques cannot describe the mechanistic steps at molecular level for interfaces with nanometer thicknesses. Among surface sensitive techniques, VSFG (vibrational sum frequency generation) has been utilized to study various parameters that control the formation of surfactant monolayers at water-oil interfaces. In this brief-review, basics about utilization of VSFG along with recent advances for studying the water-oil interfaces will be presented, aiming at familiarizing other scientists with the current understanding of the water-oil interfaces as studied by VSF