Marc-André Gaveau

Cluster isolated chemical reactions

The study of chemical reactions in clusters is a rapidly growing field that is attractive for investigating medium effects in reaction dynamics. Cluster isolated chemical reaction (CICR) is a new direction developed in our laboratory, which enables quantitative studies to be made in that field. CICR experiments consist in depositing a controlled number of reactants on large van der Waals clusters that play the role of a solvent of fairly well known size, structure and temperature. This offers enormous advantages, both on the experimental side and for further theoretical investigations. The present review intends to draw together informations that are pertinent for developing experiments and concepts towards understanding chemical reactions in clusters, through CICR-type experiments. In particular, it reviews the questions first of generating and controlling the properties of large van der Waals clusters and secondly of attaching reactants to clusters and controlling their number and location in the cluste...

Transition state in metal atom reactions

The observation of the transition state in metal molecule reactions has been approached by several experimental methods, crossed beams, transition state spectroscopy and more briefly via time dependent femtosecond localization. The chemistry is far richer than the one-dimensional harpoon model involving an instant single electron jump imagined at the origin.

Dynamics of highly excited barium atoms deposited on large argon clusters. I. General trends

Ba(Ar)(approximately 750) clusters were generated by associating the supersonic expansion and the pick-up techniques. A femtosecond pump (266.3 nm)-probe (792 or 399.2 nm) experiment was performed to document the dynamics of electronically excited barium within the very multidimensional environment of the argon cluster. Barium was excited in the vicinity of the 6s9p (1)P state and probed by ionization. The velocity imaging technique was used to monitor the energy distribution of photoelectrons and photoions as a function of the delay time between the pump and the probe pulses. A complex dynamics was revealed, which can be interpreted as a sequence/superposition of elementary processes, one of which is the ejection of barium out of the cluster. The latter has an efficiency, which starts increasing 5 ps after the pump pulse, the largest ejection probability being at 10 ps. The ejection process lasts at a very long time, up to 60 ps. A competing process is the partial solvation of barium in low lying electronic states. Both processes are preceded by a complex electronic relaxation, which is not fully unraveled here, the present paper being the first one in a series.

Gas phase dynamics of triplet formation in benzophenone

Benzophenone is a prototype molecule for photochemistry in the triplet state through its high triplet yield and reactivity. We have investigated its dynamics of triplet formation under the isolated gas phase conditions via femtosecond and nanosecond time resolved photoelectron spectroscopy. This represents the complete evolution from the excitation in S2 to the final decay of T1 to the ground state S0. We have found that the triplet formation can be described almost as a direct process in preparing T1, the lowest reacting triplet state, from the S1 state after S2 → S1 internal conversion. The molecule was also deposited by a pick-up technique on cold argon clusters providing a soft relaxation medium without evaporation of the molecule and the mechanism was identical. This cluster technique is a model for medium influenced electronic relaxation and provides a continuous transition from the isolated gas phase to the relaxation dynamics in solution.

Dynamics of the barium-molecule system within large argon clusters

The effects of adding molecules on the LIF at 540 nm of a barium atom at the surface of an argon cluster (average size 420) has been investigated. We showed that molecules like ethanol,n-hexane and O2 from stable complexes with ground state barium. In the case of molecules like N2, CH4 and SF6, the collisional quenching of solvated Ba(1P) is observed. The large quenching rates obtained are interpreted by a surface mobility of the collisional partners. Moreover, we showed that this collisional quenching leads to the ejection of free Ba(3P1).

Time resolved observation of the solvation dynamics of a Rydberg excited molecule deposited on an argon cluster-I: DABCO☆ at short times

This paper is a joint experimental and theoretical approach concerning a molecule deposited on a large argon cluster. The spectroscopy and the dynamics of the deposited molecule are measured using the photoelectron spectroscopy. The absorption spectrum of the deposited molecule shows two solvation sites populated in the ground state. The combined dynamics reveals that the population ratio of the two sites is reversed when the molecule is electronically excited. This work provides the timescale of the corresponding solvation dynamics. Theoretical calculation supports the interpretation. More generally, close examination of the short time dynamics (0-6 ps) of DABCO···Ar(n) gives insights into the ultrafast relaxation dynamics of molecules deposited at interfaces and provides hence the time scale for deposited molecules to adapt to their neighborhoods.

Spectroscopy and dynamics of calcium dimers deposited on large argon and neon van der Waals clusters

Laser-induced-fluorescence studies of calcium dimer deposited on large argon and neon clusters have been performed. The spectroscopy of the Ca2 A state is slightly perturbed by the cluster surface leading to shifts and broadenings of the order or less than 100 cm−1. An absorption has been evidenced in the 530–550 nm wavelength range that is tentatively assigned to the yet undocumented A ′1Πu state of Ca2 correlating to the Ca(1D)+Ca(1S) asymptotic limit. The excited calcium dimer dynamics are very different in neon and argon clusters. The argon cluster is much more efficient for electronic and vibrational relaxation of the excited dimer. Finally, excitation in the blue of the calcium atomic resonance line leads to a competition between dissociation of the dimer with ejection of an excited calcium atom out of the cluster and the relaxation of the dimer to lower excited levels.

Unsupervised joint decomposition of a spectroscopic signal sequence

This paper addresses the problem of decomposing a sequence of spectroscopic signals. Data are a series of signals modeled as a noisy sum of parametric peaks. We aim to estimate the peak parameters given that they change slowly between two contiguous signals. The key idea is to decompose the whole sequence rather than each signal independently. The problem is set within a Bayesian framework. The peaks with similar evolution are gathered into groups and a Markovian prior on the peak parameters of a same group is used to favor a smooth evolution of the peaks. In addition, the peak number and the group number are unknown and have to be estimated (the number of peaks in two contiguous signals change if peaks vanish). Therefore, the posterior distribution is sampled with a reversible jump Markov chain Monte Carlo algorithm. Simulations conducted on synthetic and real photoelectron data illustrate the performance of the method. HighlightsThis work aims at estimating the parameters of Gaussian peaks in spectroscopic signals.Data gather actually several spectroscopic signals, so the decomposition is performed jointly on the whole data.The peaks evolve slowly through the data and may appear and disappear.We propose an original Bayesian model and an implementation of the RJMCMC algorithm.The performances of the method are discussed on synthetic and real (photoelectron) data.

Spectral characterization in a supersonic beam of neutral chlorophyll a evaporated from spinach leaves

The observation of the light absorption of neutral biomolecules has been made possible by a method implemented for their preparation in the gas phase, in supersonically cooled molecular beams, based upon the work of Focsa et al. [C. Mihesan, M. Ziskind, B. Chazallon, E. Therssen, P. Desgroux, S. Gurlui, and C. Focsa, Appl. Surf. Sci. 253, 1090 (2006)]. The biomolecules diluted in frozen water solutions are entrained in the gas plume of evaporated ice generated by an infrared optical parametric oscillators (OPO) laser tuned close to its maximum of absorption, at ~3 μm. The biomolecules are then picked up in the flux of a supersonic expansion of argon. The method was tested with indole dissolved in water. The excitation spectrum of indole was found cold and large clusters of indole with water were observed up to n = 75. Frozen spinach leaves were examined with the same method to observe the chlorophyll pigments. The Q(y) band of chlorophyll a has been observed in a pump probe experiment. The Q(y) bands of chlorophyll a is centred at 647 nm, shifted by 18 nm from its position in toluene solutions. The ionization threshold could also be determined as 6.1 ± 0.05 eV.

Transition-state spectroscopy of the photoinduced Ca + CH3F reaction. 3. Reaction following the local excitation to Ca(4s3d 1D).

The Ca* + CH3F --> CaF* + CH3 reaction was studied both experimentally and theoretically. The reaction was photoinduced in Ca...CH3F complexes, which were illuminated by a tunable laser in the range 18 000-24 000 cm-1. The absorption band that leads to the reaction extends between 19 000 and 23 000 cm-1. It is formed of three broad overlapping structures corresponding to the excitation of different electronic states of the complex. The two structures of lowest energy were considered in detail. They are associated with two series of respectively 2 and 3 molecular states correlating to Ca(4s3d 1D) + CH3F at infinite separation between Ca and CH3F. The assignment of these structures to specific electronic transitions of the complex stemmed from theoretical calculations where the Ca...CH3F complex is described by a linear Ca-F-C backbone. 2D potential energy surfaces were calculated by associating a pseudopotential description of the [Ca2+] and [F7+] cores, a core polarization operator on calcium, an extensive Gaussian basis, and a treatment of the electronic problem at the CI-MRCI level. All the excited levels correlating to the 4s2 1S, 4s3d 1D, and 4s4p 1P levels of Ca in the Ca + CH3F channel were documented in a calculation that explored the rearrangement channels where either Ca + CH3F or CaF + CH3 are formed. Then, wavepacket calculations on the 2D-PESs allowed one to simulate the absorption spectrum of the complex, in an approximation where the various electronic states of the complex are not coupled together. The assignment above stemmed from this. The second outcome of the calculation was that whatever the excited level of the complex that is considered, the reaction has to proceed through energy barriers. The electronic excitation of the complex on the red side of the absorption band does not seem to deposit enough energy in the system to overcome these barriers (even the lowest one) or to stimulate tunneling reactions. An alternative reaction mechanism involving a transfer to triplet PESs is proposed.