WORKPLAN FOR THE REACTIVE INTERMEDIATES NETWORK, Nov2000

WORKPLAN FOR THE REACTIVE INTERMEDIATES NETWORK, Nov 2000

     The first Network meeting was held in Amsterdam in October 2000. All groups in the Network were represented. It was agreed that the next Network meeting will be held in Lisbon in April 2001.
     A plan was proposed for future Network meetings, which will be held approximately every six months, as follows:-

Garching, Crete, Southampton, Orsay, Bremen and Salisbury

     It is proposed that preparation for the Mid-Term Review will take place at the Southampton meeting, which will also incorporate a team-building/presentation course for the Young Researchers (YRs). The Mid-Term review will be held at the Orsay meeting.
If it proves necessary to hold the Mid-Term review in Orsay earlier, the order of the meetings will be changed to

Garching, Southampton, Orsay, Crete, Bremen and Salisbury

     The appointment of YRs was discussed and the YR applications that had been received were reviewed. It was recognised that more applications were required from good quality YRs and it was decided that each team leader would prepare an advert for the vacancy in their laboratory and send it to the Co-ordinator for advertising on appropriate newsletter Web-sites. Minutes were taken at the meeting and will be placed on the Network Homepage by the Network Manager when these have been finalised.

     The Workplan was discussed at the meeting in some detail and finalised for the first 12 months of the project. A draft workplan was also specified for the later years.
The Workplan for each participating group can be summarised as follows:-

Southampton

Year 1
Start UVPES studies of azide pyrolysis (in collaboration with the Lisbon group) and start PES studies of reactions of atomic and molecular chlorine atoms with atmospherically important sulphur compounds.
Year 2
Start REMPI studies of small radicals in collaboration with the Amsterdam group and continue with the azide studies with Lisbon.
Year 3
REMPI and ZEKE studies of small hydrocarbon radicals (in collaboration with the Orsay group) and continue with the collaboration with the Amsterdam group on small diatomic and triatomic radicals.
     Electronic structure calculations will continue throughout this work.

Amsterdam

Year 1
REMPI-PES experiments will be started in collaboration with the Crete, Orsay and Southampton groups on small radicals, including NFand ClO. Ion-molecule reaction studies will be initiated using ICR-FTMS with Garching and Salisbury (this will continue throughout the three years).
Year 2
The results obtained on NF and ClO will be analysed and REMPI-PES experiments will be started on NCl and BrO, in collaboration with the Southampton group. Also work on small carbon containing radicals will be initiated in collaboration with Orsay. Sub-picosecond REMPI-PES experiments will also be performed on these radicals. The second half of the year will be allocated to working on clusters of atmospheric importance (e.g. NO(H₂O)_n or O₂(H₂O)_n) in collaboration with the Garching group) .
Year 3
This will be allocated to detailed analysis of the results obtained in the previous year. Electronic structure calculations performed in Southampton will be useful here. Experiments will be initiated with the Crete group to study sulphur-containing radicals, and with the Lisbon group to study decomposition of selected azides by REMPI-PES to detect and investigate the electronic structure of the imine and nitrene intermediates.

Orsay

Year 1
The photodissociation mechanisms of C₂H₂ will be studied via Rydberg states using multiphoton excitation and VUV excitation methods. Dispersed fluorescence and REMPI will be used to study the radicals produced and MPI of the lightest fragment (H) will be used to measure the energy released, for dissociation processes which produce hydrogen atoms. This work will involve the groups of Amsterdam and Crete.
Year 2
Polyaromatic hydrocarbon (PAH) radicals and ions will be studied using electronic spectroscopy with 2-photon, 2-colour resonant ionisation. Again the groups of Amsterdam and Crete will be involved.
Year 3
At least half of the year will be allocated to detailed analysis of the results obtained on these collaborative projects, involving Orsay, Crete and Amsterdam. Some theoretical input will be obtained from Southampton. Also, Cavity Ring Down Spectroscopy (CRDS) will be used to investigate the vibrational and electronic spectroscopy of radicals produced by photodissociation of acetylene (e.g. C₂H).

Forth, Crete

Year 1
State-to-state dynamics of high lying Rydberg states of CS₂, OCS, and acetylene will be studied using one and/or two colour REMPI-TOF and PES. Photodissociation via selected excited states of these molecules will be studied using a pump/probe femtosecond laser system. The acetylene work will be in collaboration with the Orsay group.
Year 2
Investigations on the photodynamics of Cl₂O will be undertaken using a pump/probe femtosecond laser system in collaboration with Amsterdam. Also, the photodissocation and ionization behaviour of PAH species will be studied in collaboration with Orsay and Amsterdam. Some experiments on the photodissociation of selected azoalkanes and alkyl nitrites will be performed in collaboration with the Lisbon group.
Year 3
These experiments will continue in Year 3, with at least half the year being allocated to analysis of the results obtained in collaboration with Lisbon, Orsay and Amsterdam.

DERA, Salisbury

Year 1
For at least the first six months, proton transfer reactions to volatile and involatile organophosphates will be studied using an ESI-ITMS instrument. This work would complement related work using high temperature ion mobility spectrometry and an FTMS instrument will be used for elemental analysis of ions of unknown composition. This work will be performed in collaboration with the Amsterdam group. Then, in the next six months reactions of mass selected cationic and anionic water clusters with nitric oxide and sulphurous oxide will be studied using an ICR-FTMS instrument. This work will be performed in collaboration with Garching and Amsterdam. Computational support will be provided by Southampton.
Year 2
The first six months will be mainly devoted to analysis and interpretation of the results obtained. Electronic structure calculations performed in Southampton will be needed here. In the second half of the year, the nature of some reactions of the O^- and O₂^- ions will be investigated. Reactions will be investigated in SIFT-FA and ICR-FTMS instruments and the target molecules will be selected from some atmospherically important molecules (e.g. halogenated hydrocarbons). These experiments will be performed in conjunction with the studies of reactions of solvated anions in Garching and will assist in understanding the role of anions in the atmosphere.
Year 3
Reactions of O^- and CO₃^- with selected CFCs and PFCs will be investigated both in a SIFT spectrometer and by ICR-FTMS. Garching will also be involved in performing related experiments involving reactions of O^- and CO₃^-with CFCs and PFCs. Theoretical support for this work will be provided by Southampton.

Lisbon

Year 1
The postdoctoral fellow involved in this project will study selected aliphatic azides, as well as some azoalkanes and alkyl nitrites, by UVPES. The Southampton group will be involved in this work by assisting with initial experiments and spectral interpretation. Some of the compounds under study will also be investigated by the Amsterdam and Crete groups by studying their photodissociation behaviour via selected excited states.
Year 2
The first six months will be required for the research fellow to analyse and interpret the results obtained, in collaboration with Southampton, Amsterdam and Crete. Then surface adsorption characterization of some aliphatic azides, azoalkanes and nitrites and selected fluorinated compounds on selected surfaces such as Ag(111) and Pt/Rh will be studied using XPS and SIMS.
Year 3
Reactions of CO and O₂, and NO_x with N₂, will be investigated on Ni.La and Pt/Rh surfaces.Adsorption-desorption reactions will be studied as a function of temperature down to 77K. Electron and ion stimulated processes will be studied by XPS and SIMS. The work performed on the decomposition of selected alphatic azides on Ag(111) and Pt/Rh sufaces will overlap with studies of the interaction of aliphatic azides with metal clusters performed in Garching.

Garching

Year 1
To study reactivity of large water clusters ions, a variable temperature shield will be designed for an ICR cell. Close contact will be maintained with Dr Baykut (Bruker Daltonik GmbH) during this period for technical advice. Reactivity of large mass-selected cationic and anionic water clusters with nitric oxide and sulphurous acid will then be studied. Complementary studies will be performed at Salisbury at higher pressures. Attempts will also be made to study mass selected ionic-clusters in matrices using infrared spectroscopy.
Year 2
This six month period will be devoted mainly to analysis of the results obtained. The research fellow will also spend some time in Southampton gaining experience of theoretical methods and applying ab initio and density functional methods to assist interpretation of the results obtained. Then the reactivity of mass-selected chlorinated water clusters with hydrogen chloride and chlorine nitrate will be studied to help to understand the role of chlorine chemistry in polar stratospheric clouds. Complementary studies will be performed in Salisbury.
Year 3
The experiments on mass-selected chlorinated water cluster ions will continue. Also, experiments will be performed in collaboration with the Salisbury group to study reactions of solvated O^- and O₂^- with molecules of atmospheric importance. This will extend to study reactions of O^- and CO₃^-, and their hydrated forms, with CFCs and PFCs. Southampton will be involved with the interpretation of the results.

Bruker-Daltonik GmbH

     Dr Baykut and colleagues will maintain regular contact with the research teams involved in the Network and will attend all Network meetings.
     The main aim is for Bruker to advise on operation and improvement of existing instruments. If major developments are made as part of the project, then Bruker will have the option of incorporating these into new or existing instruments.
     Bruker has agreed to take one postdoctoral fellow from the Network for one month each year during the project period. Initial interaction in Year 1 will be mainly with the Garching group, with the postdoctoral fellow working at Bruker (in Bremen) to test a variable temperature ICR cell for use in experiments on large water cluster ions.
     Later interaction will occur with other participating teams involved in mass spectrometry (i.e. Lisbon, Salisbury and Amsterdam)----for example, an interaction with Salisbury and Amsterdam will occur in the use of an electrospray instrument for less volatile organophosphates and will extend later to other participating groups.