Ultrafast relaxation of photoexcited superfluid He nanodroplets

The relaxation of photoexcited nanosystems is a fundamental process of light-matter interaction. Depending on the couplings of the internal degrees of freedom, relaxation can be ultrafast, converting electronic energy in a few fs, or slow, if the energy is trapped in a metastable state that decouples from its environment. Here, we study helium nanodroplets excited resonantly by femtosecond extreme-ultraviolet (XUV) pulses from a seeded free- electron laser. Despite their superfluid nature, we find that helium nanodroplets in the lowest electronically excited states undergo ultrafast relaxation. By comparing experimental pho- toelectron spectra with time-dependent density functional theory simulations, we unravel the full relaxation pathway: Following an ultrafast interband transition, a void nanometer-sized bubble forms around the localized excitation (He ) within 1 ps. Subsequently, the bubble collapses and releases metastable He at the droplet surface. This study highlights the high level of detail achievable in probing the photodynamics of nanosystems using tunable XUV pulses

Vibrational Spectroscopy of Microhydrated Conjugate Base Anions

Conjugate-base anions are ubiquitous in aqueous solution. Understanding the hydration of these anions at the molecular level represents a long-standing goal in chemistry. A molecular-level perspective on ion hydration is also important for understanding the surface speciation and reactivity of aerosols, which are a central component of atmospheric and oceanic chemical cycles. In this Account, as a means of studying conjugate-base anions in water, we describe infrared multiple-photon dissociation spectroscopy on clusters in which the sulfate, nitrate, bicarbonate, and suberate anions are hydrated by a known number of water molecules. This spectral technique, used over the range of 550–1800 cm–1, serves as a structural probe of these clusters. The experiments follow how the solvent network around the conjugate-base anion evolves, one water molecule at a time. We make structural assignments by comparing the experimental infrared spectra to those obtained from electronic structure calculations. Our results show how changes in anion structure, symmetry, and charge state have a profound effect on the structure of the solvent network. Conversely, they indicate how hydration can markedly affect the structure of the anion core in a microhydrated cluster. Some key results include the following. The first few water molecules bind to the anion terminal oxo groups in a bridging fashion, forming two anion–water hydrogen bonds. Each oxo group can form up to three hydrogen bonds; one structural result, for example, is the highly symmetric, fully coordinated SO42–(H2O)6 cluster, which only contains bridging water molecules. Adding more water molecules results in the formation of a solvent network comprising water–water hydrogen bonding in addition to hydrogen bonding to the anion. For the nitrate, bicarbonate, and suberate anions, fewer bridging sites are available, namely, three, two, and one (per carboxylate group), respectively. As a result, an earlier onset of water–water hydrogen bonding is observed. When there are more than three hydrating water molecules (n > 3), the formation of a particularly stable four-membered water ring is observed for hydrated nitrate and bicarbonate clusters. This ring binds in either a side-on (bicarbonate) or top-on (nitrate) fashion. In the case of bicarbonate, additional water molecules then add to this water ring rather than directly to the anion, indicating a preference for surface hydration. In contrast, doubly charged sulfate dianions are internally hydrated and characterized by the closing of the first hydration shell at n = 12. The situation is different for the –O2C(CH2)6CO2– (suberate) dianion, which adapts to the hydration network by changing from a linear to a folded structure at n > 15. This change is driven by the formation of additional solute–solvent hydrogen bonds

Photodissociation spectroscopy and dynamics of the vinoxy (CH{sub 2}CHO) radical

The photodissociation spectroscopy and dynamics of the vinoxy (CH{sub 2}CHO) radical have been studied using fast beam photofragment translational spectroscopy. The photodissociation cross section over the B{sup 2}A{double_prime} {l_arrow} X{sup 2}A{double_prime} band is measured, and photofragment translational energy and angular distributions are obtained at several excitation energies. For CH{sub 2}CHO, predissociation is observed over the entire band, including several transitions near the band origin which were seen previously in laser-induced fluorescence experiments. Two dissociation channels are seen: CH{sub 3} + CO and H + CH{sub 2}CO. The CH{sub 3} + CO channel was investigated in considerable detail and appears to proceed via internal conversion to the CH{sub 2}CHO ground state followed by isomerization to CH{sub 3}CO and subsequent dissociation. The translational energy distributions for this channel suggest an isomerization barrier in the range of 2 eV with respect to CH{sub 3} + CO products