Pseudo-Jahn-Teller origin of the low barrier hydrogen bond in N2H7+

The microscopic origin and quantum effects of the low barrier hydrogen bond (LBHB) in the proton-bound ammonia dimer cation N2H7+ were studied by means of ab initio and density-functional theory(DFT) methods. These results were analyzed in the framework of vibronic theory and compared to those obtained for the Zundel cation H5O2+. All geometry optimizations carried out using wavefunction-based methods [Hartree–Fock, second and fourth order Möller–Plesset theory (MP2 and MP4), and quadratic configuration interaction with singles and doubles excitations (QCISD)] lead to an asymmetrical H3N–H+⋯NH3 conformation (C3v symmetry) with a small energy barrier (1.26kcal/mol in MP4 and QCISD calculations) between both equivalent minima. The value of this barrier is underestimated in DFT calculations particularly at the local density approximation level where geometry optimization leads to a symmetric H3N⋯H+⋯NH3 structure (D3d point group). The instability of the symmetric D3d structure is shown to originate from the pseudo-Jahn–Teller mixing of the electronic A1g1ground state with five low lying excited states of A2u symmetry through the asymmetric α2u vibrational mode. A molecular orbital study of the pseudo-Jahn–Teller coupling has allowed us to discuss the origin of the proton displacement and the LBHB formation in terms of the polarization of the NH3 molecules and the transfer of electronic charge between the proton and the NH3 units (rebonding). The parallel study of the H5O2+ cation, which presents a symmetric single-well structure, allows us to analyze why these similar molecules behave differently with respect to proton transfer. From the vibronic analysis, a unified view of the Rudle–Pimentel three-center four-electron and charge transfer models of LBHBs is given. Finally, the large difference in the N–N distance in the D3d and C3v configurations of N2H7+ indicates a large anharmonic coupling between α2u-α1g modes along the proton-transfer dynamics. This issue was explored by solving numerically the vibrational Schrödinger equation corresponding to the bidimensional E[Q(α2u),Q(α1g)] energy surface calculated at the MP4/6-311++G** level of theory

COPD classification models and mortality prediction capacity

Our aim was to assess the impact of comorbidities on existing COPD prognosis scores. Patients and methods: A total of 543 patients with COPD (FEV1 < 80% and FEV1/ FVC <70%) were included between January 2003 and January 2004. Patients were stable for at least 6 weeks before inclusion and were followed for 5 years without any intervention by the research team. Comorbidities and causes of death were established from medical reports or information from primary care medical records. The GOLD system and the body mass index, obstruction, dyspnea and exercise (BODE) index were used for COPD classification. Patients were also classified into four clusters depending on the respiratory disease and comorbidities. Cluster analysis was performed by combining multiple correspondence analyses and automatic classification. Receiver operating characteristic curves and the area under the curve (AUC) were calculated for each model, and the DeLong test was used to evaluate differences between AUCs. Improvement in prediction ability was analyzed by the DeLong test, category-free net reclassification improvement and the integrated discrimination index. Results: Among the 543 patients enrolled, 521 (96%) were male, with a mean age of 68 years, mean body mass index 28.3 and mean FEV1% 55%. A total of 167 patients died during the study follow-up. Comorbidities were prevalent in our cohort, with a mean Charlson index of 2.4. The most prevalent comorbidities were hypertension, diabetes mellitus and cardiovascular diseases. On comparing the BODE index, GOLDABCD, GOLD2017 and cluster analysis for pre-dicting mortality, cluster system was found to be superior compared with GOLD2017 (0.654 vs 0.722, P=0.006), without significant differences between other classification models. When cardiovascular comorbidities and chronic renal failure were added to the existing scores, their prognostic capacity was statistically superior (P<0.001). Conclusion: Comorbidities should be taken into account in COPD management scores due to their prevalence and impact on mortalit

Chronic obstructive pulmonary disease subtypes. transitions over time

Background Although subtypes of chronic obstructive pulmonary disease are recognized, it is unknown what happens to these subtypes over time. Our objectives were to assess the stability of cluster-based subtypes in patients with stable disease and explore changes in clusters over 1 year. Methods Multiple correspondence and cluster analysis were used to evaluate data collected from 543 stable patients included consecutively from 5 respiratory outpatient clinics. Results Four subtypes were identified. Three of them, A, B, and C, had marked respiratory profiles with a continuum in severity of several variables, while the fourth, subtype D, had a more systemic profile with intermediate respiratory disease severity. Subtype A was associated with less dyspnea, better health-related quality of life and lower Charlson comorbidity scores, and subtype C with the most severe dyspnea, and poorer pulmonary function and quality of life, while subtype B was between subtypes A and C. Subtype D had higher rates of hospitalization the previous year, and comorbidities. After 1 year, all clusters remained stable. Generally, patients continued in the same subtype but 28% migrated to another cluster. Together with movement across clusters, patients showed changes in certain characteristics (especially exercise capacity, some variables of pulmonary function and physical activity) and changes in outcomes (quality of life, hospitalization and mortality) depending on the new cluster they belonged to Conclusions Chronic obstructive pulmonary disease clusters remained stable over 1 year. Most patients stayed in their initial subtype cluster, but some moved to another subtype and accordingly had different outcomes

Adopting yield-improving practices to meet maize demand in Sub-Saharan Africa without cropland expansion

Maize demand in Sub-Saharan Africa is expected to increase 2.3 times during the next 30 years driven by demographic and dietary changes. Over the past two decades, the area croppedwithmaize has expanded by 17million hectares in the region, with limited yield increase. Following this trend could potentially result in further maize cropland expansion and the need for imports to satisfy domestic demand. Here, we use data collected from 14,773 smallholder fields in the region to identify agronomic practices that can improve farm yield gains. We find that agronomic practices related to cultivar selection, and nutrient, pest, and crop management can double on-farm yields and provide an additional 82 million tons of maize within current cropped area. Research and development investments should be oriented towards agricultural practices with proven capacity to raise maize yields in the region

Origin of Small Barriers in Jahn–Teller Systems:Quantifying the Role of 3d–4s Hybridization in the Model System NaCl:Ni⁺

Despite its relevance, the microscopic origin of the energy barrier, B, between the compressed and elongated geometries of Jahn–Teller (JT) systems is not well understood yet because of a lack of quantitative data about its various contributions. Seeking to clear up this matter, we have carried out both periodic and cluster ab initio calculations on the model system NaCl:Ni+. This system is particularly puzzling because, according to experimental data, its barrier is much smaller than that for other d9 and d7 ions in similar lattices. All calculations performed on the model system lead, in fact, to values |B| ≤ 160 cm–1, which are certainly smaller than B = 500 cm–1 derived for NaCl:M2+ (M = Ag, Rh) or B = 1024 cm–1 obtained for KCl:Ag2+. As a salient feature, analysis of calculations carried out as a function of the Qθ (3z2 – r2) coordinate unveils the microscopic origin of the barrier. It is quantitatively proven that the elongated geometry observed for NaCl:Ni+ is due to the 3d–4s vibronic admixture, which is slightly larger than the anharmonicity in the eg JT mode that favors a compressed geometry. The existence of these two competing mechanisms explains the low value of B for the model system, contrary to cases where the complex formed by d9 or d7 ions is elastically decoupled from the host lattice. Although the magnitude of B for NaCl:Ni+ is particularly small, the tunneling splitting, 3Γ, is estimated to be below 9 cm–1, thus explaining why the coherence is easily destroyed by random strains and thus a static JT effect is observed experimentally. As a main conclusion, the barrier in JT systems cannot be understood neglecting the tiny changes of the electronic density involved in small distortions. The present calculations reasonably explain the experimental g tensor of NaCl:Ni+, pointing out that the d–d transitions in NiCl65– are much smaller than those for CuCl64– and the optical electronegativity of Ni+ is only around 1.</p