Direct observation of photoionization dynamics in solution phase induced by femtosecond two-photon excitation

In solution phase, the solute can be photo-ionized in the lower excitation energy than its ionization potential in gas phase. Therefore, the specific interaction is expected to be exist between the surrounding media and higher excited (Sn) state of the solute. In order to elucidate such polarization effect of solvent on the photoionization process, femtosecond double-pulse excitation was applied to direct detection of low-energy photoionization dynamics of a phenylenediamine derivative in solution phase. From the results of the transient absorption change, in polar solvent, it is clearly indicated that photoionization does not proceed directly from the Sn state, but through specific intermediate state. Moreover,

Relaxed structure of typical nitro explosives in the excited state: observation, implication and application

<a></a><a></a><a></a><a>U</a><a></a><a></a><a></a><a></a><a></a><a>nderstanding the structural, geometrical and chemical changes that occur after electronic excitation is essential to unraveling the inherent mechanism of nitro explosives. In this work, relaxed structures of typical nitro explosives in the excited state are investigated by time-dependent density functional theory. During the excitation process, nitro group becomes activated and then relaxes, leading to a relaxed structure. </a><a></a><a>All five nitro explosives exhibit a similar behavior, and impact sensitivity is related to excitation energy of relaxed structure.</a> <a></a><a>H</a>igh sensitivity d-HMX has a lower excitation energy for relaxed structure than b-HMX. This work offers a novel insight into energetic material.<a></a>

Long-term spectroscopic monitoring of LBVs and LBV candidates

We present results of a long-term spectroscopic monitoring program (since mid 2009) of Luminous Blue Variables with the new HERMES echelle spectrograph on the 1.2m Mercator telescope at La Palma (Spain). We investigate high-resolution (R = 80,000) optical spectra of two LBVs, P Cyg and HD 168607, the LBV candidates MWC 930 and HD 168625, and the LBV binary MWC 314. In P Cyg we observe flux changes in the violet wings of the Balmer Hα, Hβ, and He i lines between May and Sep 2009. The changes around 200 to 300 km s−1 are caused by variable opacity at the base of the supersonic wind from the blue supergiant.We observe in MWC 314 broad double-peaked metal emission lines with invariable radial velocities over time. On the other hand, we measure in the photospheric S ii λ5647 absorption line, with lower excitation energy of ~14 eV, an increase of the heliocentric radial velocity centroid from 37 km s−1 to 70 km s−1 between 5 and 10 Sep 2009 (and 43 km s−1 on 6 Apr 2010). The increase of radial velocity of ~33 km s−1 in only 5 days can confirm the binary nature of this LBV close to the Eddington luminosity limit.A comparison with VLT-UVES and Keck-Hires spectra observed over the past 13 years reveals strong flux variability in the violet wing of the Hα emission line of HD 168625 and in the absorption portion of the Hβ line of HD 168607. In HD 168625 we observe Hα wind absorption at velocities exceeding 200 km s−1 which develops between Apr and June 2010.

Excitation Energy Dependence in Near-infrared Photoluminescence Spectra and Dynamics of PuO22+ in Cs2U(Pu)O2Cl4

Recently we reported the observation of near-infrared photoluminescence from metal-centered 5f electronic excited states of PuO22+ doped into polycrystalline Cs2U(Pu)O2Cl4.[1] Photoluminescence dynamics following pulsed excitation show complicated decay patterns suggesting that multiple luminescent states are involved. Here we report the results of two recent sets of experiments showing that photoluminescence processes depend significantly on the energy of photoexcitation. In the first case, decay kinetics following excitation at a lower energy are missing an in-growth term that is present when exciting at higher energy. In the second case, we have observed that lower excitation energy produces significantly reduced number of emission transitions than higher excitation energy. Both observations suggest that higher energy excitation populates feeder states that decay to emitting states, causing signal from the latter to have an in-growth followed by a decay characteristic of their intrinsic lifetimes, whereas lower energy excitation leads to more direct population of luminescent states.