Crystalline and correlated phases in two-dimensional transition metal dichalcogenides

This thesis is dedicated to the study of various aspects of the electronic structure of two-dimensional transition metal dichalcogenides (TMDs) of chemical composition MX$_2$ (where M is a transition metal atom and X= S, Se, Te), using a combination of \textit{ab inito} density-functional methods. We first address the relative stability of the $1T$ and $1H$ phases of two-dimensional TMDs as a function of the column of the transition metal atom in the periodic table. Using a Wannier-function approach, we calculate crystal field and ligand field parameters for a broad range of members of this family of materials. Taking TaS$_2$ as an example, we show how the splitting of the $d$ electron states arises from an interplay of electrostatic effects and hybridization with the ligands' $s$, $p$ and $d$ states. We show that the ligand field alone cannot explain the stabilization of the $1H$ polymorph for $d^1$ and $d^2$ TMDs, and that band structure effects are dominant. We present trends of the calculated parameters across the periodic table, and argue that these allow developing simple chemical intuition. Secondly, we study the occurrence of charge density wave phases and periodic lattice distortion in metallic $1T$ transition metal dichalcogenides. The phonon dispersion and fermiology of representative examples with different $d$ electron counts are studied as a function of doping. Two qualitatively different behaviours are found as a function of the filling of the $t_{2g}$ subshell. We argue that away from half-filling, weak-coupling nesting arguments are a useful starting point for understanding, whereas closer to half-filling a strong-coupling real-space picture is more correct. Using Wannier functions, it is shown that strong metal-metal bonds are formed and that simple bond-counting arguments apply. Thirdly, the recently synthesized $1T$ phase of NbSe$_2$, in monolayer form, is investigated from first principles. We find that $1T$-NbSe$_2$ is unstable towards the formation of an incommensurate charge density wave phase, whose periodicity can be understood from the Fermi surface topology. We investigate different scenarios for the experimentally observed superlattice and insulating behaviour, and conclude that the star-of-David phase is the most stable commensurate charge density wave phase. We study the electronic properties of the star-of-David phase at various levels of theory and confirm its Mott insulating character, as speculated and in analogy with TaS$_2$. The Heisenberg exchange couplings are found to be ferromagnetic, which suggests a parallel with the so-called flat-band ferromagnetism in certain multiband Hubbard models. Finally, we address the possibility of the occurrence of the excitonic insulator phase in single-layer TiSe$_2$. The relative role of electron-electron and electron-phonon interactions in driving the charge density wave in layered and two-dimensional TiSe$_2$ has been disputed and is still unresolved. We calculate the electronic structure and finite-momentum exciton spectrum from hybrid density functional theory. We find that in a certain range of parameters, excitonic effects are strong and the material is close to a pure excitonic insulator instability. A possible necessary condition for the physical realization of a pure excitonic insulator is proposed

Disorder engineering and conductivity dome in ReS2 with electrolyte gating

Atomically thin rhenium disulphide (ReS2) is a member of the transition metal dichalcogenide (TMDC) family of materials characterized by weak interlayer coupling and a distorted 1T structure. Here, we report on the electrical transport study of mono- and multilayer ReS2 with polymer electrolyte gating. We find that the conductivity of monolayer ReS2 is completely suppressed at high carrier densities, an unusual feature unique to monolayers, making ReS2 the first example of such a material. While thicker flakes of ReS2 also exhibit a conductivity dome and an insulator-metal-insulator sequence, they do not show a complete conductivity suppression at high doping densities. Using dual-gated devices, we can distinguish the gate-induced doping from the electrostatic disorder induced by the polymer electrolyte itself. Theoretical calculations and a transport model indicate that the observed conductivity suppression can be explained by a combination of a narrow conduction band and Anderson localization due to electrolyte-induced disorder.Comment: Submitted versio

COVID-19 symptoms at hospital admission vary with age and sex: results from the ISARIC prospective multinational observational study

Background: The ISARIC prospective multinational observational study is the largest cohort of hospitalized patients with COVID-19. We present relationships of age, sex, and nationality to presenting symptoms. Methods: International, prospective observational study of 60 109 hospitalized symptomatic patients with laboratory-confirmed COVID-19 recruited from 43 countries between 30 January and 3 August 2020. Logistic regression was performed to evaluate relationships of age and sex to published COVID-19 case definitions and the most commonly reported symptoms. Results: ‘Typical’ symptoms of fever (69%), cough (68%) and shortness of breath (66%) were the most commonly reported. 92% of patients experienced at least one of these. Prevalence of typical symptoms was greatest in 30- to 60-year-olds (respectively 80, 79, 69%; at least one 95%). They were reported less frequently in children (≤ 18 years: 69, 48, 23; 85%), older adults (≥ 70 years: 61, 62, 65; 90%), and women (66, 66, 64; 90%; vs. men 71, 70, 67; 93%, each P < 0.001). The most common atypical presentations under 60 years of age were nausea and vomiting and abdominal pain, and over 60 years was confusion. Regression models showed significant differences in symptoms with sex, age and country. Interpretation: This international collaboration has allowed us to report reliable symptom data from the largest cohort of patients admitted to hospital with COVID-19. Adults over 60 and children admitted to hospital with COVID-19 are less likely to present with typical symptoms. Nausea and vomiting are common atypical presentations under 30 years. Confusion is a frequent atypical presentation of COVID-19 in adults over 60 years. Women are less likely to experience typical symptoms than men

Multiancestry analysis of the HLA locus in Alzheimer’s and Parkinson’s diseases uncovers a shared adaptive immune response mediated by HLA-DRB1*04 subtypes

Across multiancestry groups, we analyzed Human Leukocyte Antigen (HLA) associations in over 176,000 individuals with Parkinson’s disease (PD) and Alzheimer’s disease (AD) versus controls. We demonstrate that the two diseases share the same protective association at the HLA locus. HLA-specific fine-mapping showed that hierarchical protective effects of HLA-DRB1*04 subtypes best accounted for the association, strongest with HLA-DRB1*04:04 and HLA-DRB1*04:07, and intermediary with HLA-DRB1*04:01 and HLA-DRB1*04:03. The same signal was associated with decreased neurofibrillary tangles in postmortem brains and was associated with reduced tau levels in cerebrospinal fluid and to a lower extent with increased Aβ42. Protective HLA-DRB1*04 subtypes strongly bound the aggregation-prone tau PHF6 sequence, however only when acetylated at a lysine (K311), a common posttranslational modification central to tau aggregation. An HLA-DRB1*04-mediated adaptive immune response decreases PD and AD risks, potentially by acting against tau, offering the possibility of therapeutic avenues

30-Day Morbidity and Mortality of Bariatric Surgery During the COVID-19 Pandemic: a Multinational Cohort Study of 7704 Patients from 42 Countries.

BACKGROUND There are data on the safety of cancer surgery and the efficacy of preventive strategies on the prevention of postoperative symptomatic COVID-19 in these patients. But there is little such data for any elective surgery. The main objectives of this study were to examine the safety of bariatric surgery (BS) during the coronavirus disease 2019 (COVID-19) pandemic and to determine the efficacy of perioperative COVID-19 protective strategies on postoperative symptomatic COVID-19 rates. METHODS We conducted an international cohort study to determine all-cause and COVID-19-specific 30-day morbidity and mortality of BS performed between 01/05/2020 and 31/10/2020. RESULTS Four hundred ninety-nine surgeons from 185 centres in 42 countries provided data on 7704 patients. Elective primary BS (n = 7084) was associated with a 30-day morbidity of 6.76% (n = 479) and a 30-day mortality of 0.14% (n = 10). Emergency BS, revisional BS, insulin-treated type 2 diabetes, and untreated obstructive sleep apnoea were associated with increased complications on multivariable analysis. Forty-three patients developed symptomatic COVID-19 postoperatively, with a higher risk in non-whites. Preoperative self-isolation, preoperative testing for SARS-CoV-2, and surgery in institutions not concurrently treating COVID-19 patients did not reduce the incidence of postoperative COVID-19. Postoperative symptomatic COVID-19 was more likely if the surgery was performed during a COVID-19 peak in that country. CONCLUSIONS BS can be performed safely during the COVID-19 pandemic with appropriate perioperative protocols. There was no relationship between preoperative testing for COVID-19 and self-isolation with symptomatic postoperative COVID-19. The risk of postoperative COVID-19 risk was greater in non-whites or if BS was performed during a local peak

Safety of Bariatric Surgery in ≥ 65-Year-Old Patients During the COVID-19 Pandemic

Background Age >= 65 years is regarded as a relative contraindication for bariatric surgery. Advanced age is also a recognised risk factor for adverse outcomes with Coronavirus Disease-2019 (COVID-19) which continues to wreak havoc on global populations. This study aimed to assess the safety of bariatric surgery (BS) in this particular age group during the COVID-19 pandemic in comparison with the younger cohort.Methods We conducted a prospective international study of patients who underwent BS between 1/05/2020 and 31/10/2020. Patients were divided into two groups - patients >= 65-years-old (Group I) and patients < 65-years-old (Group II). The two groups were compared for 30-day morbidity and mortality.Results There were 149 patients in Group 1 and 6923 patients in Group II. The mean age, preoperative weight, and BMI were 67.6 +/- 2.5 years, 119.5 +/- 24.5 kg, and 43 +/- 7 in Group I and 39.8 +/- 11.3 years, 117.7 +/- 20.4 kg, and 43.7 +/- 7 in Group II, respectively. Approximately, 95% of patients in Group 1 had at least one co-morbidity compared to 68% of patients in Group 2 (p = < 0.001). The 30-day morbidity was significantly higher in Group I ( 11.4%) compared to Group II (6.6%) (p = 0.022). However, the 30-day mortality and COVID-19 infection rates were not significantly different between the two groups.Conclusions Bariatric surgery during the COVID-19 pandemic is associated with a higher complication rate in those >= 65 years of age compared to those < 65 years old. However, the mortality and postoperative COVID-19 infection rates are not significantly different between the two groups