Transient coherent Raman scattering in the time and frequency domain

A new type of Raman spectroscopy is presented: After transient excitation of molecular modes coherently scattered Raman spectra are investigated in a depayed probing experiment. The spectral position of the Raman mode is observed after long delay times. The dephasing time is obtained from the time dependence of the scattered amplitudes. Frequency disturbing non-resonant susceptibilities are eliminated. We report on first experimental results of transient coherent Raman spectroscopy of liquid CH3CCl3

A new Raman technique of superior spectral resolution

Raman-active vibrational modes are coherently excited by the transient stimulated Raman process. A subsequent delayed probe of relatively long duration interacts with the freely relaxing vibrations. Raman spectra are generated with higher resolution and more accurate peak positions than in conventional Raman spectroscopy. In liquid cyclohexane four new Raman lines were readily detected in the frequency range 2870–2920 cm−1

Terahertz quantum beats in molecular liquids

With ultrashort pulses of less than 100 fs it is possible to excite coherently several vibrational modes of polyatomic molecules simultaneously. The femtosecond time resolution of the experiment allows the study of pronounced high-frequency beat phenomena up to 10 THz. The frequency difference between vibrational modes separated by more than 300 cm−1 may be determined with high precision

Narrowing of spectral lines beyond the natural or dephasing line width

Transient excitation and gated or delayed observation provides a narrowing of the inherent line width of the transition. Possible experimental one- and two-photon systems are discussed and the loss of signal with line narrowing is calculated. The general case of lines broadened by dephasing processes is treated. Contact is made with the line narrowing in recent Raman type experiments

Generation of frequency shifted picosecond pulses with low temporal jitter

Transient stimulated Raman scattering is used for the generation of a frequency shifted picosecond light pulse; part of this Raman shifted pulse is subsequently coherently scattered at a material excitation of a second Raman cell. Starting with the second harmonic pulse (tp = 4 ps) of a mode-locked Nd : glass laser system, both the stimulated and the coherently produced pulses have durations of 2.3 ps at different wavelengths. By the appropriate choice of the Raman medium pulses between 13 000 and 21 000 cm-1 can be generated. The coherent generation process minimizes the temporal jitter between the two pulses and allows to obtain a high time resolution of better than 0.3 ps in excite and probe experiments

Vibrational lifetimes and intramolecular energy randomisation of polyatomic molecules in liquids

Transient experiments with picosecond laser pulses give valuable information on the dynamic properties of polyatomic molecules in the electronic ground state. In small molecules the decay of vibrational energy occurs via individual lower energy states; in large molecules the experimental data support a statistical model

Second harmonic beam analysis, a sensitive technique to determine the duration of single ultrashort laser pulses

The second harmonic beam generated in a noncollinear arrangement allows the observation of the autocorrelation functio: A compact optical beam splitter and imaging system eliminates alignment problems. Single pulses of 1 ps duration and approximately 10−8 joule energy are readily observed using an optical multichannel analyser

A difference detection system for high precision measurements of ultrafast transmission changes

Ultrafast transmission changes can be recorded with high precision by means of a difference detection system. Using single pulses of low energy (0.1 nJ) and low repetition rate, variations of the transmitted energy induced by an excitation pulse are measured with an accuracy of 10-4

The influence of phase-modulation on femtosecond time-resolved coherent Raman spectroscopy

The influence of phase-modulation on femtosecond time-resolved coherent Raman scattering is investigated theoretically and experimentally. The coherent Raman signal taken as a function of the spectral position shows unexpected temporal oscillations close to time zero. A theoretical analysis of the coherent Raman scattering process indicates that the femtosecond light pulses are amplitude and phase modulated. The pulses are asymmetric in time with more slowly decaying trailing wings. The phase of the pulse amplitude contains quadratic and higher-order contributions

Changes of vibrational lifetimes with minor structural modification of small polyatomic molecules

Substantial changes of population lifetimes of CH-stretching modes are observed when two atoms are exchanged in CH2=CCl2 to form trans CHCl=CHCl and when three deuterons are substituted in C6H6 to form 1,3,5.-C6H3D3. The measured lifetimes are in good agreement with estimates based on Fermi resonance-mixing which is inferred from infrared and Raman spectra