Work Package Number 1

MOLECULAR IDENTIFICATION OF VOC’s AND RADICALS RESPONSIBLE FOR THE GREENHOUSE EFFECT AND FOR POLLUTION

Start Month 1 – End Month 48

Lead Beneficiary

Key people: Leader: A.Cuisset (ULCO)

co-leaders: M.Carvajal (UHU)  and  N.Inostroza (UAC)

Participating organisations

Objectives: WP1 pursues both the theoretical and the experimental spectroscopic characterization of OVOC’s containing internal rotors, atmosphere radicals and abundant atmosphere components. WP1 deals with uncharacterized isolated targets which can play important roles in the processes related to WP2 and WP3.

Description of Work

Planned Secondments

TASK1.1- Characterization of OVOC’s containing internal rotors using FIR and THz spectroscopy, ab initio calculations and theoretical developments for spectrum assignments. In the infrared spectral range recorded by large scale instruments for molecular identification (i.e. the Atmospheric Chemistry Experiment (ACE) on board of the Canadian satellite SciSat-1; the Infrared Atmospheric Sounding Interferometer (IASI) on board of the European satellite METOP-A), many spectra of molecules with internal rotors are waiting for a complete theoretical modelling that includes vibration-rotation-torsional coupling to reproduce the high resolution infrared spectra with high precision, and to provide reliable line-lists for the atmospheric community.

The approach we will follow is both experimental and theoretical, combining microwave, far-infrared and infrared measurements (all available at CNRS, ULCO or other collaborations), possibly using the very bright synchrotron radiation if the torsional bands are too weak to be recorded with usual sources, and cooling down the sample to decrease the line density. Highly correlated ab initio calculations (CSIC, UMV, USTHB,UAC) and program codes for determining ab initio spectroscopic constants (CSIC) will be useful to complement the effective Hamiltonians used to model the data (UHU,CNRS).

TASK1.2. Spectroscopic characterization of atmosphere radicals: Through photochemical processes VOC’s can be precursors of atmosphere radicals relevant for the chemical evolution. Using laboratory techniques (high resolution IR spectroscopy and microwave techniques in the millimeter and submillimeter wavelength ranges (ULCO, CNRS) in connection with theoretical procedures (ab initio calculations and theoretical models for nuclear motion), these species can be characterized.  The collaboration between CSIC, UHU, CNRS, ULCO, BUW, UMV, USTHB, UAC, CQU and the exchange of young researchers can facilitate these studies. The groups of BUW and UHU have developed theoretical procedures for detailed studies. Accurate ab initio calculations, suitable for describing non-adiabatic effects, can be used to understand the structure of the excited electronic states and to characterize the electronic states involved in the different photolysis mechanisms. UHU, BUW, UMV, USTHB, UAC and CQU can collaborate in these studies. Some of the selected radicals will be object of photochemical studies corresponding to WP2.

TASK1.3. Spectroscopic characterization of abundant atmosphere components: The previous collaboration involving BUW have led to the installation and sustained 24/7 operation of a EU-regulation conforming air monitoring station (O₃, CO, CO₂, NO, NO₂, SO₂, PM2.5, PM10). Within the framework of this proposal it is envisioned to extend these activities into developing on the calculation of high-resolution ro-vibrational spectra of small molecules relevant to atmospheric processes in collaboration with the CSIC, UHU, BUW, UAC, USTHB and UMV groups. This approach would pave the way for numerous in-depth studies for the application of computational methods at various levels relevant to a broad variety of applications. Computational methods are of particular interest, since the generation, exchange, and treatment of data is not necessarily depending on the local availability of powerful hardware but rather broad band-width internet connections, which are available and fully functional.

TASK1.4. Dissemination in scientific journals, conferences and data base.

Work Package Number 2

REACTIVE PROCESSES OF ATMOSPHERIC RADICALS: RADICAL CYCLES AND PHOTODISSOCIATION

Start Month 1 – End Month 48

Lead Beneficiary

Key people: Leader: A. García Vela (CSIC)

co-leaders: C. Coeur (ULCO), W.Chen (ULCO)

Participating organisations

Objectives: WP2 deals with reactive processes and pursues the theoretical study of the mechanisms and photodissociation pathways of radical species and the study of the roles of organic peroxy (RO₂) radical reactions in atmospheric degradation of volatile organic compounds (VOCs) through laboratory techniques.

Description of Work

Planned Secondments

T2.1 The theoretical study of the photodissociation pathways and mechanisms of radical species: Organic radicals can be found in the atmosphere produced by several processes, most of them through dissociative processes of OVOC’s. Furthermore, photodissociation of these radicals produces additional atmosphere pollutants following radical cycles that are not fully understood. The goal of this study is threefold. 1) The characterization of the electronic states involved in the different photolysis mechanisms. This objective is also common to WP1. 2) The calculation of the relevant potential-energy surfaces (PES) associated with these electronic states by using high quality and highly correlated ab initio methodologies. 3) Once the electronic states playing a role in the photodissociation processes and their corresponding PESs are characterized, the photodissociation dynamics will be simulated when possible, in order to obtain dynamical properties to provide a better understanding of the photochemical processes of interest. These simulations will be carried out by employing quantum mechanical dynamical methodologies developed in CSIC. The tasks involved in the above studies will be carried out by the groups of CSIC, UHU, UMV, UAC, and USTHB. These groups have a large expertise in the ab initio and quantum dynamical methodologies required to perform the studies programmed. The group of CSIC works in collaboration with the laboratory of Chemical Reaction Dynamics and Femtochemistry, in Universidad Complutense de Madrid.

T2.2 The study of the roles of organic peroxy (RO₂) radicals reactions in atmospheric degradation of volatile organic compounds (VOCs): The work will follow different steps: 1) kinetic studies will be performed in a flow tube reactor (with on-line spectroscopy instruments for real time measurement of free radicals, and high resolution mass spectroscopy/synchrotron radiation photoionization mass spectrometry for the monitoring of the reaction products and precursors); 2) Experimental studies and modelling of the degradation of VOC’s in simulation chambers (CASHIPS, ULCO). Simultaneous measurements of RO₂ radicals and other key intermediate oxygenated VOC’s will improve the accuracy the models; 3) Field measurement will also be performed for a quantitative study of the effect of VOC’s degradation on the production of atmospheric fine particles and O₃. All these techniques are available in the CASHIPS and the ULCO institutions. The work will be performed in collaboration between CASHIPS and the ULCO group. Ab initio calculations on radicals, which is an important objective of WP1 (groups UMV and USTHB), can help the understanding and the modelling of the processes.

Work Package Number 3

UNDERSTANDING OF GAS-GAS AND GAS-SOLID INTERACTIONS: APPLICATIONS

Start Month 1 – End Month 48

Lead Beneficiary

Key people: Leader: D. Benoit

co-leaders: M.G. Francesconi (UHULL), J.M. Fernández (CSIC) and V. Timón  (CSIC)

Participating organisations

Objectives: WP3 deals with non-reactive interactions. It pursues the study of rotationally-inelastic collisions of pairs of small atmosphere components, the modelling of silicate aerosols. WP3 also deals with theoretical and experimental studies of gas-solid interactions towards the design of new materials for gas sequestration.

Description of Work

Planned Secondments

T3.1. Study of rotationally-inelastic collisions of pairs of small atmosphere components: Raman spectroscopy of supersonic gas jets can be employed along with the study of rotationally-inelastic collisions of pairs of small atmosphere components such as N₂+O₂ and CO₂+CO₂. Number densities and rotational populations can be directly measured from the rotational and/or vibrational Raman spectra along the jet axis. From these primary data, rotational and translational temperatures can be obtained, the latter from conservation of mass, momentum, and enthalpy. These measurements can be linked to calculations of state-to-state rate coefficients (sts-rates) by means of the kinetic Master Equation, which accounts for the time evolution of the rotational populations. Studies require both laboratory experiments (CSIC) and quantum chemical calculations to determine interaction potential energy surfaces (UMV and USTHB). Previous spectroscopic studies of monomers are mandatory. In the case of CO₂, WP1 includes the rotational and rovibrational study (UHU).

T3.2 Understanding of gas-solid interactions focused on greenhouse gas sequestration: design of new materials. The understanding of gas-solid interactions is mandatory for greenhouse gas sequestration. Gas sequestration using solids (for example CaO and zeolites) is an emerging field; we will bring it forward by designing novel materials that can be efficient, cheap and resilient. One of the WP3 objectives is the exploitation of some of GHG as reagents towards the preparation of innovative materials, contributing, at the same time, to the reduction of their presence in the environment. UHULL will have the tasks to prepare new inorganic solids for the capture of gases such as CO₂, CH_4, ...etc, along with their structural analysis. It will also validate a vibrational model for captured molecules, explore reaction paths in solid state and use intelligent design to develop new capture materials. CSIC will develop a classical interaction model of ionic solids suitable to describe molecule capture and participate in the elaboration of reaction paths for capture processes. UMV and USTHB will determine the structural parameters of physi-sorbed gas molecules and then determine the reaction path for adsorbed gases.

T3.3 Modelling of Phyllosilicates and gas-solid interactions in mineral dust particles (leader Timón): Aerosols can take active part in processes such as heterogeneous chemical reactions. Many atmospheric particles are formed by a solid core (in large proportion formed by silicate particles created by erosion of the soils), onto which molecules can be adsorbed. The nucleation ability of the particles depends on many factors, both intrinsic to the particle composition and surface type and external or environmental, such as temperature and humidity. Phyllosilicates (smectite group, bentonites, kaolinite and micas, abundant clay materials, ...) are particularly interesting for atmosphere studies because they can be taken as witnesses for the presence of water. These species, which include water in their composition, are produced by aqueous alterations of other primeval minerals. For their remote detection it is essential to count with laboratory measurements, supported by theoretical modeling. This task will be carried out using computation techniques in collaboration with laboratory techniques of French collaborators. This task requires the collaboration between CSIC (solid state simulation) and UMV and USTHB (theoretical calculations).

Work Package Number 6

TRAINING ACTIVITIES

Start Month 1 – End Month 48

Lead Beneficiary

Key people: Leader: I. Kleiner (CNRS)

co-leader: N- Komiha (UMV)

Participating organisations

Objectives: WP6 pursuits to improve the career perspectives of the ERs and ESRs involved in this project

Description of Work

T6.1 ATMOS WINTER School (ATMOS-WS) represents the main training activity. It will be organized in Rabat, by UMV. The main local organizer will be N. Komiha.

T6.2 The participation of ERs and especially ESRs in the two workshops organized in the framework of this project (Workshops I and II). In the case WORKSHOP I, ERS will attend to the talks, and they will be also encouraged to participate with poster presentations.  In Workshop II ERS will be encouraged to present their own work in the form of oral and poster presentations, as well as to discuss it with other guest researchers. These activities are intended to promote and enhance the scientific autonomy of the ESRs.

T6.3. Co-supervised PhD Thesis: within the frame of the MSCA CAPZEO, researchers of two different partner institutions co-supervised a total of 5 PhD Thesis. The exchange of PhD students within ATMOS project can be a new opportunity that has relevance for future careers and formation.  We consider that ATMOS represents a unique opportunity for visiting Europe for the students of the partner group. Some of their countries have a very short scientific history. Their visit to the European laboratories not only represents an opportunity to increase the scientific knowledge but also means an opportunity to know how organize and manage a laboratory. Their participation in the dissemination and impact activities can improve their view of the scientific world. 

T6.4 Generation of reports for research papers and competitive projects. The ESRs will be encouraged to write the manuscripts reporting the results obtained with the work carried out during their secondments, and that will be submitted to the appropriate scientific research journals. In addition, the ESRs will be encouraged and trained to prepare reports and memos to be submitted in order to apply for different types of funded competitive projects. We consider these activities as an essential part of their training as future researchers

T6.5 Participation in dissemination and communication activities. Participation of the ESRs in dissemination and communication activities during the entire project will be fostered as an important part of their training. For this purpose, participation of the ESRs in the dissemination and communication strategies, designed to achieve the highest visibility of the work they have carried out in the framework of ATMOS among the different audiences relevant to the project, will be actively pursued.