Validation of the TROPOspheric Monitoring Instrument (TROPOMI) surface UV radiation product

The TROPOspheric Monitoring Instrument (TROPOMI) onboard the Sentinel-5 Precursor (S5P) satellite was launched on 13 October 2017 to provide the atmospheric composition for atmosphere and climate research. The S5P is a Sun-synchronous polar-orbiting satellite providing global daily coverage. The TROPOMI swath is 2600 km wide, and the ground resolution for most data products is 7:23:5 km2 (5:63:5 km2 since 6 August 2019) at nadir. The Finnish Meteorological Institute (FMI) is responsible for the development of the TROPOMI UV algorithm and the processing of the TROPOMI surface ultraviolet (UV) radiation product which includes 36 UV parameters in total. Ground-based data from 25 sites located in arctic, subarctic, temperate, equatorial and Antarctic areas were used for validation of the TROPOMI overpass irradiance at 305, 310, 324 and 380 nm, overpass erythemally weighted dose rate/UV index, and erythemally weighted daily dose for the period from 1 January 2018 to 31 August 2019. The validation results showed that for most sites 60 % 80% of TROPOMI data was within 20% of ground-based data for snow-free surface conditions. The median relative differences to ground-based measurements of TROPOMI snow-free surface daily doses were within 10% and 5% at two-Thirds and at half of the sites, respectively. At several sites more than 90% of cloud-free TROPOMI data was within 20% of groundbased measurements. Generally median relative differences between TROPOMI data and ground-based measurements were a little biased towards negative values (i.e. satellite data ground-based measurement), but at high latitudes where non-homogeneous topography and albedo or snow conditions occurred, the negative bias was exceptionally high: from 30% to 65 %. Positive biases of 10 % 15% were also found for mountainous sites due to challenging topography. The TROPOMI surface UV radiation product includes quality flags to detect increased uncertainties in the data due to heterogeneous surface albedo and rough terrain, which can be used to filter the data retrieved under challenging conditions

The post-Born-Oppenheimer regime: dynamics of electronic motion in molecules by attosecond few-cycle spectroscopy

Dynamics of electronic motion when the nuclei are clamped is discussed and shown to be always described as a superposition of adiabatic electronic states. These states are stationary when the nuclei are clamped but their superposition leads to multiply periodic motion where the natural frequencies are the differences in the energies of the adiabatic electronic states. When one or more of the frequencies are low and the atoms are allowed to move, the electronic rearrangement is commensurate with the motion of the nuclei. This is the usual breakdown of the Born-Oppenheimer approximation. But when the electronic frequencies are higher there is an electronic motion before the nuclei move. The motion can be demonstrated through expectation values such as the multipole moments of the charge distribution. Such superposition states will be excited when the laser pulse width in energy exceeds the spacings of the states. For low-lying valence excited or low Rydberg states this requires a femtosecond or shorter laser pulse. Since the carrier frequency has to be comparable to the excitation energy, the required laser pulses must span only a few cycles

On the strong and selective isotope effect in the UV excitation of N2 with implications toward the nebula and Martian atmosphere

Isotopic effects associated with molecular absorption are discussed with reference to natural phenomena including early solar system processes, Titan and terrestrial atmospheric chemistry, and Martian atmospheric evolution. Quantification of the physicochemical aspects of the excitation and dissociation processes may lead to enhanced understanding of these environments. Here we examine a physical basis for an additional isotope effect during photolysis of molecular nitrogen due to the coupling of valence and Rydberg excited states. The origin of this isotope effect is shown to be the coupling of diabatic electronic states of different bonding nature that occurs after the excitation of these states. This coupling is characteristic of energy regimes where two or more excited states are nearly crossing or osculating. A signature of the resultant isotope effect is a window of rapid variation in the otherwise smooth distribution of oscillator strengths vs. frequency. The reference for the discussion is the numerical solution of the time dependent Schrödinger equation for both the electronic and nuclear modes with the light field included as part of the Hamiltonian. Pumping is to all extreme UV dipole-allowed, valence and Rydberg, excited states of N2. The computed absorption spectra are convoluted with the solar spectrum to demonstrate the importance of including this isotope effect in planetary, interstellar molecular cloud, and nebular photochemical models. It is suggested that accidental resonance with strong discrete lines in the solar spectrum such as the CIII line at 97.703 nm can also have a marked effect