The collisional depolarization of OH(A 2Σ+) and NO(A 2Σ+) with Kr

Quantum beat spectroscopy has been used to measure rate coefficients at 300 K for collisional depolarization for NO(A 2Σ+) and OH(A 2Σ+) with krypton. Elastic depolarization rate coefficients have also been determined for OH(A) + Kr, and shown to make a much more significant contribution to the total depolarization rate than for NO(A) + Kr. While the experimental data for NO(A) + Kr are in excellent agreement with single surface quasiclassical trajectory (QCT) calculations carried out on the upper 2A ′ potential energy surface, the equivalent QCT and quantum mechanical calculations cannot account for the experimental results for OH(A) + Kr collisions, particularly at low N. This disagreement is due to the presence of competing electronic quenching at low N, which requires a multi-surface, non-adiabatic treatment. Somewhat improved agreement with experiment is obtained by means of trajectory surface hopping calculations that include non-adiabatic coupling between the ground 1A ′ and excited 2A ′ states of OH(X/A) + Kr, although the theoretical depolarization cross sections still significantly overestimate those obtained experimentally

Clonal chromosomal mosaicism and loss of chromosome Y in elderly men increase vulnerability for SARS-CoV-2

The pandemic caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2, COVID-19) had an estimated overall case fatality ratio of 1.38% (pre-vaccination), being 53% higher in males and increasing exponentially with age. Among 9578 individuals diagnosed with COVID-19 in the SCOURGE study, we found 133 cases (1.42%) with detectable clonal mosaicism for chromosome alterations (mCA) and 226 males (5.08%) with acquired loss of chromosome Y (LOY). Individuals with clonal mosaic events (mCA and/or LOY) showed a 54% increase in the risk of COVID-19 lethality. LOY is associated with transcriptomic biomarkers of immune dysfunction, pro-coagulation activity and cardiovascular risk. Interferon-induced genes involved in the initial immune response to SARS-CoV-2 are also down-regulated in LOY. Thus, mCA and LOY underlie at least part of the sex-biased severity and mortality of COVID-19 in aging patients. Given its potential therapeutic and prognostic relevance, evaluation of clonal mosaicism should be implemented as biomarker of COVID-19 severity in elderly people. Among 9578 individuals diagnosed with COVID-19 in the SCOURGE study, individuals with clonal mosaic events (clonal mosaicism for chromosome alterations and/or loss of chromosome Y) showed an increased risk of COVID-19 lethality

Surface-hopping trajectories for OH(A(2)Σ(+)) + Kr: Extension to the 1A″ state

We present a new trajectory surface hopping study of the rotational energy transfer and collisional quenching of electronically excited OH(A) radicals by Kr. The trajectory surface hopping calculations include both electronic coupling between the excited 2(2)A' and ground 1(2)A' electronic states, as well as Renner-Teller and Coriolis roto-electronic couplings between the 1(2)A' and 1(2)A″, and the 2(2)A' and 1(2)A″ electronic states, respectively. The new calculations are shown to lead to a noticeable improvement in the agreement between theory and experiment in this system, particularly with respect to the OH(X) rotational and Λ-doublet quantum state populations, compared with a simpler two-state treatment, which only included the electronic coupling between the 2(2)A' and 1(2)A' states. Discrepancies between the predictions of theory and experiment do however remain, and could arise either due to errors in the potential energy surfaces and couplings employed, or due to the limitations in the classical treatment of non-adiabatic effects

Experimental and theoretical studies of the Xe-OH(A/X) quenching system

New multi-reference, global ab initio potential energy surfaces (PESs) are reported for the interaction of Xe atoms with OH radicals in their ground X2Π and excited A2Σ+ states, together with the non-adiabatic couplings between them. The 2A' excited potential features a very deep well at the collinear Xe-OH configuration whose minimum corresponds to the avoided crossing with the 1A' PES. It is therefore expected that, as with collisions of Kr + OH(A), electronic quenching will play a major role in the dynamics, competing favorably with rotational energy transfer within the 2A' state. The surfaces and couplings are used in full three-state surface-hopping trajectory calculations, including roto-electronic couplings, to calculate integral cross sections for electronic quenching and collisional removal. Experimental cross sections, measured using Zeeman quantum beat spectroscopy, are also presented here for comparison with these calculations. Unlike similar previous work on the collisions of OH(A) with Kr, the surface-hopping calculations are only able to account qualitatively for the experimentally observed electronic quenching cross sections, with those calculated being around a factor of two smaller than the experimental ones. However, the predicted total depopulation of the initial rovibrational state of OH(A) (quenching plus rotational energy transfer) agrees well with the experimental results. Possible reasons for the discrepancies are discussed in detail

Electronic Quenching of OH A 2Σ+ Induced by Collisions with Kr Atoms

Electronic quenching of OH A (2)Σ(+) by Kr was investigated through experimental studies of the collision cross sections and the OH X (2)Π product state distribution. The quenching cross sections decrease with increasing rotational excitation in the excited OH A (2)Σ(+) electronic state. The OH X (2)Π products of quenching exhibit a significant degree of rotational excitation but minimal vibrational excitation. Complementary theoretical studies of the OH (A (2)Σ(+), X (2)Π) + Kr potential energy surfaces (PESs), nonadiabatic coupling, and quasiclassical trajectory calculations were carried out to elucidate the quenching dynamics. Accurate PESs for the two lowest diabatic states of A' symmetry were computed along with the angularly dependent coupling between them. Coupling in nearly linear HO-Kr configurations provides the mechanism for the observed electronic quenching. A deep attractive well on the OH A (2)Σ(+) + Kr PES facilitates access to this region of strong coupling. Surface-hopping quasiclassical trajectory calculations yielded quenching cross sections and a OH X (2)Π product rotational distribution in good accord with experimental observations

The collisional depolarization of OH(A ²Σ⁺) and NO(A ²Σ⁺) with Kr

Quantum beat spectroscopy has been used to measure rate coefficients at 300 K for collisional depolarization for NO(A 2Σ+) and OH(A 2Σ+) with krypton. Elastic depolarization rate coefficients have also been determined for OH(A) + Kr, and shown to make a much more significant contribution to the total depolarization rate than for NO(A) + Kr. While the experimental data for NO(A) + Kr are in excellent agreement with single surface quasiclassical trajectory (QCT) calculations carried out on the upper 2A ′ potential energy surface, the equivalent QCT and quantum mechanical calculations cannot account for the experimental results for OH(A) + Kr collisions, particularly at low N. This disagreement is due to the presence of competing electronic quenching at low N, which requires a multi-surface, non-adiabatic treatment. Somewhat improved agreement with experiment is obtained by means of trajectory surface hopping calculations that include non-adiabatic coupling between the ground 1A ′ and excited 2A ′ states of OH(X/A) + Kr, although the theoretical depolarization cross sections still significantly overestimate those obtained experimentally