Tunable frequency-controlled isolated attosecond pulses characterized by either 750 nm or 400 nm wavelength streak fields.

A compact and robust Mach-Zehnder type interferometer coupled with the double optical gating technique provides tunable isolated attosecond pulses and streak field detection with fields centered at either 750 nm or 400 nm. Isolated attosecond pulses produced at 45 eV (with measured pulse duration of 114 ± 4 as) and 20 eV (with measured pulse duration of 395 ± 6 as) are temporally characterized with a 750 nm wavelength streak field. In addition, an isolated 118 ± 10 as pulse at 45 eV is measured with a 400 nm wavelength streak field. The interferometer design used herein provides broad flexibility for attosecond streak experiments, allowing pump and probe pulses to be specified independently. This capability is important for studying selected electronic transitions in atoms and molecules.

Measurement and optimization of isolated attosecond pulse contrast.

An experimental method is presented to experimentally measure and control the carrier-envelope-phase (CEP)-dependent pulse-energy contrast of isolated attosecond pulses. By scanning the CEP and measuring the photoelectron spectrum produced by the combined action of the attosecond pulses and the high-harmonic driving laser pulses at zero relative time delay, one can extract the pulse-energy ratio between the main attosecond pulse and its neighboring satellite pulses arriving in preceding or subsequent half-cycles of the driver pulse. Moreover, this method allows fast and efficient in situ retrieval of the optimal CEP for high-contrast isolated attosecond pulse generation.

Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH+allene reaction.

These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH2CCH2OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193 nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl+CH2CCH2OH photofragments, a spin-orbit branching ratio for Cl(2P1/2):Cl(2P3/2) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH2CCH2OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH2CCH2OH radical intermediate to the three most important product channels for the OH+allene reaction expected from this radical intermediate: formaldehyde+C2H3, H+acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH3 product channel. We compare our results to a previous theoretical study of the O+allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates.

Photodissociation pathways of 1,1-dichloroacetone.

We present a comprehensive investigation of the dissociation dynamics following photoexcitation of 1,1-dichloroacetone (CH(3)COCHCl(2)) at 193 nm. Two major dissociation channels are observed: cleavage of a C-Cl bond to form CH(3)C(O)CHCl + Cl and elimination of HCl. The branching between these reaction channels is roughly 9:1. The recoil kinetic energy distributions for both C-Cl fission and HCl elimination are bimodal. The former suggests that some of the radicals are formed in an excited electronic state. A portion of the CH(3)C(O)CHCl photoproducts undergo secondary dissociation to give CH(3) + C(O)CHCl. Photoelimination of Cl(2) is not a significant product channel. A primary C-C bond fission channel to give CH(3)CO + CHCl(2) may be present, but this signal may also be due to a secondary dissociation. Data from photofragment translational spectroscopy with electron impact and photoionization detection, velocity map ion imaging, and UV-visible absorption spectroscopy are presented, along with G3//B3LYP calculations of the bond dissociation energetics.