Yves Caudano

Pumping picosecond optical parametric oscillators by a pulsed Nd:YAG laser mode locked using a nonlinear mirror

We report on the performances of the mode locking of a flash-lamp-pumped Nd:YAG laser using a frequency-doubling nonlinear mirror combined with a two-photon absorber. Pulse lengths from 12 to 8 ps are generated. We show that the flat shape of the pulse-train envelope generated by the oscillator is adapted for the synchronous pumping of optical parametric oscillators and we demonstrate the efficient generation of an infrared beam tunable from 3800 to 1100 cm−1 with bandwidth of 2 cm−1 in one single conversion stage in LiNbO3 or AgGaS2. The “all-solid-state” laser system enables surface sum-frequency generation spectroscopy to be performed with high sensitivity and high resolution.

Development of a two-color picosecond optical parametric oscillator, pumped by a Nd:YAG laser mode locked using a nonlinear mirror, for doubly-resonant sum frequency generation spectroscopy

Abstract We set up a doubly-resonant sum frequency generation (DR-SFG) spectrometer based on the use of an all-solid-state flash-lamp-pumped Nd:YAG laser that synchronously pumps two parametric oscillators. Pulses as short as 12 ps FWHM are generated by mode locking a Nd:YAG oscillator using a frequency doubling nonlinear mirror combined with a two-photon absorber. The available pump power is shared between a LiNbO 3 /AgGaS 2 optical parametric oscillator (OPO), tunable from 3800 to 1100 cm −1 and a BBO OPO tunable from 410 to 2600 nm. Spectral resolution and pulse are 2 and 3 cm −1 in the infrared and visible spectral ranges, respectively. First DR-SFG spectra of self-assembled monolayers on Au are presented.

Orientational analysis of dodecanethiol and p-nitrothiophenol SAMs on metals with polarisation-dependent SFG spectroscopy.

Polarisation-dependent sum frequency generation (SFG) spectroscopy is used to investigate the orientation of molecules on metallic surfaces. In particular, self-assembled monolayers (SAMs) of dodecanethiol (DDT) and of p-nitrothiophenol (p-NTP), grown on Pt and on Au, have been chosen as models to highlight the ability of combining ppp and ssp polarisations sets (representing the polarisation of the involved beams in the conventional order of SFG, Vis and IR beam) to infer orientational information at metallic interfaces. Indeed, using only the ppp set of data, as it is usually done for metallic surfaces, is not sufficient to determine the full molecular orientation. We show here that simply combining ppp and ssp polarisations enables both the tilt and rotation angles of methyl groups in DDT SAMs to be determined. Moreover, for p-NTP, while the SFG active vibrations detected with the ppp polarisation alone provide no orientational information, however, the combination with ssp spectra enables to retrieve the tilt angle of the p-NTP 1,4 axis. Though orientational information obtained by polarisation-dependent measurements has been extensively used at insulating interfaces, we report here their first application to metallic surfaces.

Theoretical simulation of vibrational sum-frequency generation spectra from density functional theory: application to p-nitrothiophenol and 2,4-dinitroaniline.

The molecular orientation of adsorbed molecules forming self-assembled monolayers can be determined by combining vibrational sum-frequency generation (SFG) measurements with quantum chemical calculations. Herein, we present a theoretical methodology used to simulate the SFG spectra for different combinations of polarizations. These simulations are based on calculations of the IR vectors and Raman tensors, which are obtained from density functional theory computations. The dependency of the SFG vibrational signature with respect to the molecular orientation is presented for the molecules p-nitrothiophenol and 2,4-dinitroaniline. It is found that a suitable choice of basis set as well as of exchange-correlation (XC) functional is mandatory to correctly simulate the SFG intensities and consequently provide an accurate estimation of the adsorbed molecule orientation. Comparison with experimental data shows that calculations performed at the B3LYP/6-311++G(d,p) level of approximation provide good agreement with experimental frequencies, and with IR and Raman intensities. In particular, it is demonstrated that polarization and diffuse functions are compulsory for reproducing the IR and Raman spectra, and consequently vibrational SFG spectra, of systems such as p-nitrothiophenol. Moreover, the investigated XC functionals reveal their influence on the relative intensities, which show rather systematic variations with the amount of Hartree-Fock exchange. Finally, further aspects of the modeling are revealed by considering the frequency dependence of the Raman tensors.

IR-visible sum-frequency vibrational spectroscopy of Biphenyl-3 methylene thiol monolayer on gold and silver: effect of the visible wavelength on the SFG spectrum

Abstract We measured IR–visible sum-frequency generation spectra of CH3–(C6H4)2–(CH2)3–S–H (Biphenyl-3) self-assembled monolayers on a silver and a gold substrate. For the latter substrate, we observed different interference patterns between the resonant signal of the CH vibration and the non-resonant contribution of the substrate as a function of the visible beam wavelength. The non-linear response of the gold substrate is enhanced around 480 nm corresponding to the s–d interband transition. Such effect is not observed for the silver substrate the interband transition of which is located out of the investigated visible spectral range of 450–700 nm.

Characterization of the C60Ag(111) interface by sum-frequency generation

The C60Ag(111) interface is studied by infrared reflection absorption (IRAS) and infrared-visible sum-frequency generation (SFG) spectroscopies for infrared frequencies between 1300 and 1500 cm−1. Both IRAS and SFG spectroscopies reveal a vibrational mode located around 1445 cm−1. This mode is assigned to the Ag(2) “pentagonal pinch” mode of C60, which, although being Ramanactive and infrared-inactive in the free molecule, becomes infrared-active upon adsorption of the molecule.

Electron–phonon couplings at C60 interfaces: a case study by two-color, infrared–visible sum–frequency generation spectroscopy

Abstract We demonstrate the ability of doubly resonant sum–frequency generation (DR-SFG) to investigate electron–phonon couplings at C 60 –metal interfaces. Due to its coupling to electronic transitions, the totally symmetric A g (2) vibration of C 60 exhibits a huge enhancement of its nonlinear response for sum–frequency energies above the molecular electronic gap. We attribute this resonance to the coupling of the pentagonal pinch mode with the t 1u lowest unoccupied molecular orbital (LUMO) of C 60 .

Density functional theory-based simulations of sum frequency generation spectra involving methyl stretching vibrations: effect of the molecular model on the deduced molecular orientation and comparison with an analytical approach

The knowledge of the first hyperpolarizability tensor elements of molecular groups is crucial for a quantitative interpretation of the sum frequency generation (SFG) activity of thin organic films at interfaces. Here, the SFG response of the terminal methyl group of a dodecanethiol (DDT) monolayer has been interpreted on the basis of calculations performed at the density functional theory (DFT) level of approximation. In particular, DFT calculations have been carried out on three classes of models for the aliphatic chains. The first class of models consists of aliphatic chains, containing from 3 to 12 carbon atoms, in which only one methyl group can freely vibrate, while the rest of the chain is frozen by a strong overweight of its C and H atoms. This enables us to localize the probed vibrational modes on the methyl group. In the second class, only one methyl group is frozen, while the entire remaining chain is allowed to vibrate. This enables us to analyse the influence of the aliphatic chain on the methyl stretching vibrations. Finally, the dodecanethiol (DDT) molecule is considered, for which the effects of two dielectrics, i.e. n-hexane and n-dodecane, are investigated. Moreover, DDT calculations are also carried out by using different exchange-correlation (XC) functionals in order to assess the DFT approximations. Using the DFT IR vectors and Raman tensors, the SFG spectrum of DDT has been simulated and the orientation of the methyl group has then been deduced and compared with that obtained using an analytical approach based on a bond additivity model. This analysis shows that when using DFT molecular properties, the predicted orientation of the terminal methyl group tends to converge as a function of the alkyl chain length and that the effects of the chain as well as of the dielectric environment are small. Instead, a more significant difference is observed when comparing the DFT-based results with those obtained from the analytical approach, thus indicating the importance of a quantum chemical description of the hyperpolarizability tensor elements of the methyl group.

Picosecond laser for performance of efficient nonlinear spectroscopy from 10 to 21 mm

Laser tunability from 10 to 21 microm is obtained by use of an optical parametric oscillator based on a KTP crystal followed by a difference-frequency stage with a CdSe crystal. An all-solid-state picosecond Nd:YAG oscillator mode locked by a frequency-doubling nonlinear mirror is used for synchronous pumping.

HREELS, IR and SFG investigation of undoped and doped adsorbed fullerenes

Abstract High-resolution electron-energy-loss spectroscopy was used to characterize the vibrational fingerprint of C 60 on Ag(111) and hydrogen-passivated Si(111) surfaces and to investigate the interfacial structure of a chemisorbed monolayer of C 60 on Ag(111). Complementary results from infra-red absorption spectroscopy and sum-frequency generation spectroscopy help to interpret the spectra in the range of the T 1u (4)–A g (2) peaks. Estimation of the charge transferred to the chemisorbed monolayer upon further doping with potassium is deduced from the frequency shifts of vibrational modes.