Time-resolved high-harmonic spectroscopy of ultrafast photo-isomerization dynamics

We report the first study of time-resolved high-harmonic spectroscopy (TR-HHS) of a bond-making chemical reaction. We investigate the transient change of the high harmonic signal from 1,3-cyclohexadiene (CHD), which undergoes ring-opening and isomerizes to 1,3,5-hexatriene (HT) upon photoexcitation. By associating the change of the harmonic yield with the changes of the ionization energy and vibrational frequency of the molecule due to the isomerization, we find that the electronic excited state of CHD created via two-photon absorption of 3.1 eV photons relaxes almost completely within 80 fs to the electronic ground state of CHD with vibrational excitation. Subsequently, the molecule isomerizes abruptly to HT, i.e., ring-opening occurs, around 400 fs after the excitation. The present results demonstrate that TR-HHS, which can track both the electronic and the nuclear dynamics, is a powerful tool for unveiling ultrafast photo-chemical reactions.Comment: 25 pages, 7 figure

Excited state non-adiabatic dynamics of pyrrole:A time-resolved photoelectron spectroscopy and quantum dynamics study

The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole's electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A2(\u3c0\u3c3 17) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths has previously been assumed to result predominantly in population of the bright A1(\u3c0\u3c0 17) and B2(\u3c0\u3c0 17) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole's electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B1(\u3c0\u3c3 17) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B1(\u3c0\u3c3 17) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A2(\u3c0\u3c3 17) state.Peer reviewed: YesNRC publication: Ye

Pacemaker implantation through pericardial reflections under fluoroscopic guidance: a novel approach for patients with limited venous access

Excited state intramolecular proton transfer (ESIPT) in salicylideneaniline (SA) and selected derivatives substituted in para-position of the anilino group has been investigated by femtosecond time-resolved photoelectron spectroscopy (TRPES) and time-dependent density functional theory (TDDFT). The planarity of the molecule was found to be a key parameter to describe ESIPT

Electron trajectory selection for high harmonic generation inside a short hollow fiber

The 19th harmonic beam divergences from a Ti: sapphire laser generated using a gas jet and 10-mm-long hollow fibers with bore diameters of 300 and 200 mu m were investigated. The beam quality factor M-2 of the harmonic beam generated in a 300-mu m hollow fiber was found to be better than the gas jet using the phase match including the atomic dipole phase induced by the short trajectory. On the other hand, a 200-mu m hollow fiber was found to generate a more divergent beam with a larger M-2 because of the long trajectory. The electron trajectory contributing to high harmonic generation was selected using the phase-matching process inside a short hollow fiber. (C) 2013 Optical Society of Americ

Generation of ultrashort optical pulses using multiple coherent anti-Stokes Raman scattering in a crystal at room temperature

We demonstrate Fourier synthesis of multiple coherent anti-Stokes Raman scattering signals in a LiNbO3 crystal at room temperature. The signals up to the 20th order (470-800 nm) were generated by two crossing femtosecond Ti:sapphire laser pulses. Angle dispersion of the signals was compensated into one white-continuum beam by modifying a conventional 4f configuration. Spectral phase of the signal was measured by spectral phase interferometry for direct electric-field reconstruction. Isolated pulses with 25 fs duration at 1 kHz were generated only by appropriately aligning the angle-dispersion compensator. This result opens the possibility of the generation of subfemtosecond pulses in the visible region

Spatial light modulator with an over-two-octave bandwidth from ultraviolet to near infrared

We developed a 1-pixel ultraviolet-to-near-infrared (UV-to-NIR) liquid-crystal spatial light modulator (LC-SLM) and clarified its phase modulation properties in detail, for the first time to our knowledge. The employed liquid crystal is transparent over 260-1100 nm. A phase modulation capability of 55.8 rad at 305 nm and 14.0 rad at 1000 nm is enough to compensate for UV-to-NIR nonlinear chirped pulses. The LC-SLM driving parameters of a period T=13 ms and an applied voltage VDD=7.0 V were determined. The 648-pixel extension of this new device will permit us to realize the high-power generation of single subcycle optical pulses and the direct UV-to-NIR pulse shaping

Structural dynamics of photochemical reactions probed by time-resolved photoelectron spectroscopy using high harmonic pulses

Femtosecond ring-opening dynamics of 1,3-cyclohexadiene (CHD) in gas phase upon two-photon excitation at 400 nm (=3.1 eV) was investigated by time-resolved photoelectron spectroscopy using 42 nm (=29.5 eV) high harmonic photons probing the dynamics of the lower-lying occupied molecular orbitals (MOs), which are the fingerprints of the molecular structure. After 500 fs, the photoelectron intensity of the MO constituting the C=C sigma bond (sigma(C=C)) of CHD was enhanced, while that of the MO forming the C-C sigma bond (sigma(CC)) of CHD was decreased. The changes in the photoelectron spectra suggest that the ring of CHD opens to form a 1,3,5-hexatriene (HT) after 500 fs. The dynamics of the sigma(C=C) and sigma(CC) bands between 200 and 500 fs reflects the ring deformation to a conical intersection between the 2(1)A and 1(1)A potential energy surfaces prior to the ring-opening reaction

Generation of ultrashort optical pulses in the 10 fs regime using multicolor Raman sidebands in KTaO3

We demonstrated Fourier synthesis of a new type of multiple coherent anti-Stokes Raman scatterings in KTaO3 crystal. The signals with a wavelength range of 500-750 nm were generated by two femtosecond pulses whose frequency difference was set to be a two-phonon Raman frequency. Angle dispersion of the signals was compensated into one white-continuum beam by spherical mirrors and a prism. The spectral phase, measured by spectral phase interferometry for direct electric-field reconstruction, was compensated for by carefully aligning the angle and the position of the optical components so that 13 fs isolated pulses were generated. This result shows the robustness of our scheme to produce ultrashort optical pulses