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Liquid injection field desorption ionization (LIFDI) proves the extraordinary softness of the ionization process combined with a convenient sample supply under the exclusion of moisture and air. LIFDI–mass spectrometry (MS) is used for organometallic and other seriously air-sensitive compounds forming intact ions without substantial fragmentation. Unprecedented molecular radical anions M–• are presented along with well-known intact M+• radical cations. Furthermore closed shell cations [C]+ and adduct ions like [M + H]+ or [M + Alkali]+ are gently transferred from the solid emitter surface into the gas phase. Anions [A]– or [M − H]– are accessible by LIFDI–MS at medium field strengths. Ion pairs [C]+[A]– are separately detected by positive and negative mode LIFDI–MS, respectively. Here we give an overview of the different ion types accessible by LIFDI–MS. For the first time the field ionization/desorption of solar cell electron acceptor compounds is shown to deliver M–• and M2–• radical ions.

This assessment provides a comprehensive update of the effects of changes in stratospheric ozone and other factors (aerosols, surface reflectivity, solar activity, and climate) on the intensity of ultraviolet (UV) radiation at the Earth’s surface. The assessment is performed in the context of the Montreal Protocol on Substances that Deplete the Ozone Layer and its Amendments and Adjustments. Changes in UV radiation at low- and mid-latitudes (0–60°) during the last 25 years have generally been small (e.g., typically less than 4% per decade, increasing at some sites and decreasing at others) and were mostly driven by changes in cloud cover and atmospheric aerosol content, caused partly by climate change and partly by measures to control tropospheric pollution. Without the Montreal Protocol, erythemal (sunburning) UV irradiance at northern and southern latitudes of less than 50° would have increased by 10–20% between 1996 and 2020. For southern latitudes exceeding 50°, the UV Index (UVI) would have surged by between 25% (year-round at the southern tip of South America) and more than 100% (South Pole in spring). Variability of erythemal irradiance in Antarctica was very large during the last four years. In spring 2019, erythemal UV radiation was at the minimum of the historical (1991–2018) range at the South Pole, while near record-high values were observed in spring 2020, which were up to 80% above the historical mean. In the Arctic, some of the highest erythemal irradiances on record were measured in March and April 2020. For example in March 2020, the monthly average UVI over a site in the Canadian Arctic was up to 70% higher than the historical (2005–2019) average, often exceeding this mean by three standard deviations. Under the presumption that all countries will adhere to the Montreal Protocol in the future and that atmospheric aerosol concentrations remain constant, erythemal irradiance at mid-latitudes (30–60°) is projected to decrease between 2015 and 2090 by 2–5% in the north and by 4–6% in the south due to recovering ozone. Changes projected for the tropics are ≤ 3%. However, in industrial regions that are currently affected by air pollution, UV radiation will increase as measures to reduce air pollutants will gradually restore UV radiation intensities to those of a cleaner atmosphere. Since most substances controlled by the Montreal Protocol are also greenhouse gases, the phase-out of these substances may have avoided warming by 0.5–1.0 °C over mid-latitude regions of the continents, and by more than 1.0 °C in the Arctic; however, the uncertainty of these calculations is large. We also assess the effects of changes in stratospheric ozone on climate, focusing on the poleward shift of climate zones, and discuss the role of the small Antarctic ozone hole in 2019 on the devastating “Black Summer” fires in Australia. Additional topics include the assessment of advances in measuring and modeling of UV radiation; methods for determining personal UV exposure; the effect of solar radiation management (stratospheric aerosol injections) on UV radiation relevant for plants; and possible revisions to the vitamin D action spectrum, which describes the wavelength dependence of the synthesis of previtamin D3 in human skin upon exposure to UV radiation. Graphical abstract

There are several connections between coronavirus disease 2019 (COVID-19), solar UV radiation, and the Montreal Protocol. Exposure to ambient solar UV radiation inactivates SARS-CoV-2, the virus responsible for COVID-19. An action spectrum describing the wavelength dependence of the inactivation of SARS-CoV-2 by UV and visible radiation has recently been published. In contrast to action spectra that have been assumed in the past for estimating the effect of UV radiation on SARS-CoV-2, the new action spectrum has a large sensitivity in the UV-A (315–400 nm) range. If this “UV-A tail” is correct, solar UV radiation could be much more efficient in inactivating the virus responsible for COVID-19 than previously thought. Furthermore, the sensitivity of inactivation rates to the total column ozone would be reduced because ozone absorbs only a small amount of UV-A radiation. Using solar simulators, the times for inactivating SARS-CoV-2 have been determined by several groups; however, many measurements are affected by poorly defined experimental setups. The most reliable data suggest that 90% of viral particles embedded in saliva are inactivated within ~ 7 min by solar radiation for a solar zenith angle (SZA) of 16.5° and within ~ 13 min for a SZA of 63.4°. Slightly longer inactivation times were found for aerosolised virus particles. These times can become considerably longer during cloudy conditions or if virus particles are shielded from solar radiation. Many publications have provided evidence of an inverse relationship between ambient solar UV radiation and the incidence or severity of COVID-19, but the reasons for these negative correlations have not been unambiguously identified and could also be explained by confounders, such as ambient temperature, humidity, visible radiation, daylength, temporal changes in risk and disease management, and the proximity of people to other people. Meta-analyses of observational studies indicate inverse associations between serum 25-hydroxy vitamin D (25(OH)D) concentration and the risk of SARS-CoV-2 positivity or severity of COVID-19, although the quality of these studies is largely low. Mendelian randomisation studies have not found statistically significant evidence of a causal effect of 25(OH)D concentration on COVID-19 susceptibility or severity, but a potential link between vitamin D status and disease severity cannot be excluded as some randomised trials suggest that vitamin D supplementation is beneficial for people admitted to a hospital. Several studies indicate significant positive associations between air pollution and COVID-19 incidence and fatality rates. Conversely, well-established cohort studies indicate no association between long-term exposure to air pollution and infection with SARS-CoV-2. By limiting increases in UV radiation, the Montreal Protocol has also suppressed the inactivation rates of pathogens exposed to UV radiation. However, there is insufficient evidence to conclude that the expected larger inactivation rates without the Montreal Protocol would have had tangible consequences on the progress of the COVID-19 pandemic. Graphical abstract

We describe a study of the influence of amine-containing ligands on the photoredox-relevant properties of Eu

The reactivity and dynamics of molecular systems can be explored computationally by classical trajectory calculations. The traditional approach involves fitting a functional form of a potential energy surface (PES) to the energies from a large number of electronic structure calculations and then integrating numerous trajectories on this fitted PES to model the molecular dynamics. The ever-decreasing cost of computing and continuing advances in computational chemistry software have made it possible to use electronic structure calculations directly in molecular dynamics simulations without first having to construct a fitted PES. In this "on-the-fly" approach, every time the energy and its derivatives are needed for the integration of the equations of motion, they are obtained directly from quantum chemical calculations. This approach started to become practical in the mid-1990s as a result of increased availability of inexpensive computer resources and improved computational chemistry software. The application of direct dynamics calculations has grown rapidly over the last 25 years and would require a lengthy review article. The present Account is limited to some of our contributions to methods development and various applications. To improve the efficiency of direct dynamics calculations, we developed a Hessian-based predictor-corrector algorithm for integrating classical trajectories. Hessian updating made this even more efficient. This approach was also used to improve algorithms for following the steepest descent reaction paths. For larger molecular systems, we developed an extended Lagrangian approach in which the electronic structure is propagated along with the molecular structure. Strong field chemistry is a rapidly growing area, and to improve the accuracy of molecular dynamics in intense laser fields, we included the time-varying electric field in a novel predictor-corrector trajectory integration algorithm. Since intense laser fields can excite and ionize molecules, we extended our studies to include electron dynamics. Specifically, we developed code for time-dependent configuration interaction electron dynamics to simulate strong field ionization by intense laser pulses. Our initial application of ab initio direct dynamics in 1994 was to CH2O → H2 + CO; the calculated vibrational distributions in the products were in very good agreement with experiment. In the intervening years, we have used direct dynamics to explore energy partitioning in various dissociation reactions, unimolecular dissociations yielding three fragments, reactions with branching after the transition state, nonstatistical dynamics of chemically activated molecules, dynamics of molecular fragmentation by intense infrared laser pulses, selective activation of specific dissociation channels by aligned intense infrared laser fields, angular dependence of strong field ionization, and simulation of sequential double ionization.