Reduced Photoconductivity Observed by Time-Resolved Terahertz Spectroscopy in Metal Nanofilms with and without Adhesion Layers.

Non-contact, optical time-resolved terahertz spectroscopy (TRTS) has been used to study the transient photoconductivity of nanometer-scale metallic films deposited on fused quartz substrates. Samples of 8 nm thick gold or titanium show an instrument-limited (ca. 0.5 ps) decrease in conductivity following photoexcitation due to electron-phonon coupling and subsequent increased lattice temperatures which increases charge carrier scattering. In contrast, for samples of 8 nm gold with a 4 nm adhesion layer of titanium or chromium, a ca. 70 ps rise time for the lattice temperature increase is observed. These results establish the increased transient terahertz transmission sign change of metallic compared to semiconductor materials. The results also suggest nanoscale gold films that utilize an adhesion material do not consist of distinct layers.

Detection and Electronic Structure of Naked Actinide Complexes: Rhombic-Ring (AnN)2 Molecules Stabilized by Delocalized π-Bonding.

The major products of the reaction of laser ablated and excited U atoms and N2 are the linear N≡U≡N dinitride molecule, isoelectronic with the uranyl dication, and the diatomic nitride U≡N. These molecules form novel cyclic dimers, (UN)2 and (NUN)2, with complex electronic structures, in matrix isolation experiments, which increase on UV photolysis. In addition, (NUN)2 increases at the expense of (UN)2 upon warming the codeposited matrix samples into the 20-40 K range as attested by additional nitrogen and argon matrix infrared spectra recorded after cooling the samples back to 4 or 7 K. These molecules are identified through matrix infrared spectra with nitrogen isotopic substitution and by comparing the observed matrix frequencies with those from electronic structure calculations. The dimerization is strong (theory predicts the dimer to be on the order of 100 kcal/mol more stable than the monomers), since the ground state involves 12 bonding electrons, 8 in the σ-system, and 4 in the delocalized π-system. This delocalized π bonding is present in the U, Th, La, and Hf analogues further demonstrating the interesting interplay between the 5f and 6d orbitals in actinide chemistry. The (UN)2(+) cation is also observed in solid argon, and calculations indicate that the bonding in the ring is preserved. On the other hand, the NUN dimer is of lower C2h symmetry, and the initial NUN molecules are recognizable in this more weakly bonded (ΔE = -64 kcal/mol) structure. The NThN molecules bind more strongly in the (NThN)2 dimer than the NUN molecules in (NUN)2 since NUN itself is more stable than NThN.

Infrared spectra and electronic structure calculations for NN complexes with U, UN, and NUN in solid argon, neon, and nitrogen.

Reactions of laser-ablated U atoms with N2 molecules upon codeposition in excess argon or neon at 4 K gave intense NUN and weak UN absorptions. Annealing produced progressions of new absorptions for the UN2(N2)1,2,3,4,5 and UN(N2)1,2,3,4,5,6 complexes. The neon-to-argon matrix shift decreases with increasing NN ligation and therefore the number of noble gas atoms left in the primary coordination sphere around the NUN molecule. Small matrix shifts are observed when the secondary coordination layers around the primary UN2(N2)1,2,3,4,5 and UN(N2)1,2,3,4,5,6 complexes are changed from neon-to-argon to nitrogen. Electronic structure, energy, and frequency calculations provide support for the identification of these complexes and the characterization of the N≡U≡N and U≡N core molecules as terminal uranium nitrides. Codeposition of U with pure nitrogen produced the saturated U(NN)7 complex, which UV irradiation converted to the NUN(NN)5 complex with slightly lower frequencies than found in solid argon.

Photoexcitation dynamics in films of C60 and Zn phthalocyanine with a layered nanostructure.

We elucidate photoexcitation dynamics in C(60) and zinc phthalocyanine (ZnPc) from picoseconds to milliseconds by transient absorption and time-resolved terahertz spectroscopy. Autoionization of C(60) is a precursor to photocarrier generation. Decay of the terahertz signal is due to decreasing photocarrier mobility over the first 20 ps and thereafter reflects recombination dynamics. Singlet diffusion rates in C(60) are determined by modeling the rise of ground state bleaching of ZnPc absorption following C(60) excitation. Recombination dynamics transform from bimolecular to monomolecular as the layer thickness is reduced, revealing a metastable exciplex at the C(60)/ZnPc interface with a lifetime of 150 µs.

Infrared spectra of HC[triple bond]C-MH and M-eta2-(C2H2) from reactions of laser-ablated group- 4 transition-metal atoms with acetylene.

Reactions of laser-ablated group 4 transition-metal atoms with acetylene have been carried out. The ethynyl metal hydrides (HC[triple bond]C-MH) and corresponding pi complexes (M-eta(2)-(C2H2)) are identified in the matrix infrared spectra. The observed M-H and C-M stretching absorptions show that oxidative C-H insertion readily occurs during codeposition and photolysis afterward. The absorptions from the pi complex, on the other hand, are relatively weak in the original deposition spectrum but increase dramatically in the process of annealing. The vinylidene complex, another plausible product, is not identified in this study. The observed spectra and DFT calculations both show that the back-donations from the group 4 metals to the antibonding pi* orbital of C2H2 are extensive such that the group 4 metals form unusually strong pi complexes. Thus, it is the formation of two Ti-C bonds in the group 4 systems than leads to the stronger bonding than that in the group 8 systems. While bonds form, the Ti atom is weakly bound to C2H2, and we still refer to it as a pi complex. Evidence of relativistic effects is also observed in frequency trends for the Ti, Zr, and Hf products.

Molecular engineering in symmetric end-substituted oligothiophene derivatives: analysis of condensed-phase photoemission spectra using semiempirical Hartree-Fock calculations.

The electronic structures of two series of end-capped thiophene oligomers, one set containing the electron-deficient dimesitylboryl end-cap and one containing the electron-rich triaryl amine end-cap, have been modeled using semiempirical quantum chemical calculations and the results used to assign features in the photoemission spectra of the materials in the condensed phase. For the thiophene oligomers end-capped with the electron-deficient dimesitylboryl moieties, the energy of the occupied frontier orbitals is largely governed by pi-type orbitals of the thiophene repeat units in the oligothiophene main chain. Conversely, in oligomers end-capped with electron-rich triarylamine moieties, the occupied frontier orbital energies are largely governed by orbital states of heavily mixed character associated with thiophene pi-type systems and the low-lying nitrogen lone pairs of end capping groups.

Reactions of Th and U atoms with C2H2: infrared spectra and relativistic calculations of the metallacyclopropene, actinide insertion, and ethynyl products.

Reactions of laser-ablated Th and U atoms with C(2)H(2) during condensation with excess argon at 7 K give several new product species. The metallacyclopropene, inserted hydride, and actinide ethynyl are identified from isotopic frequencies and relativistic DFT calculations. The higher-energy vinylidine isomer was not observed. These actinide metallacyclopropenes exhibit substantially stronger bonding interactions than found recently for the Pd and Pt metals. In the case of Th(C(2)H(2)) the argon matrix interaction is strong enough to reverse the computed order of states (MR-CISD) in favor of a triplet ground state for the (Ar)(n)(Th(C(2)H(2))) complex. The nature of the electronic interactions between various metal atoms and acetylene is compared and the origin of the particularly strong interaction for U and Th is traced to the higher energy of their 6d orbitals. The ThCCH and UCCH actinide ethynyl products are also observed and characterized by C[triple bond]C stretching modes 38+/-2 cm(-1) lower than acetylene itself.

Reactions of laser-ablated uranium atoms with H2O in excess argon: a matrix infrared and relativistic DFT investigation of uranium oxyhydrides.

Laser-ablated U atoms react with H2O during condensation in excess argon. Infrared absorptions at 1416.3, 1377.1, and 859.4 cm(-1) are assigned to symmetric H-U-H, antisymmetric H-U-H, and U=O stretching vibrations of the primary reaction product H(2)UO. Uranium monoxide, UO, also formed in the reaction, inserts into H2O to produce HUO(OH), which absorbs at 1370.5, 834.3, and 575.7 cm(-1). The HUO(OH) uranium(IV) product undergoes ultraviolet photoisomerization to a more stable H2UO2 uranium(VI) molecule, which absorbs at 1406.4 and 885.9 cm(-1). Several of these species, particularly H2UO2, appear to form weak Ar-coordinated complexes. The predicted vibrational frequencies, relative absorption intensities, and isotopic shifts from relativistic DFT calculations are in good agreement with observed spectra, which further supports the identification of novel uranium oxyhydrides from matrix infrared spectra.

Reactions of B atoms and clusters with NO: experimental and theoretical characterization of novel molecules containing B, N, and O.

Reactions of boron atoms and clusters with NO molecules in solid argon have been studied using matrix isolation infrared absorption spectroscopy. The reaction products were identified by isotopic substitution ((10)B, (11)B, (15)N(16)O, (14)N(18)O, and mixtures) and comparison with density functional calculations of isotopic frequencies. In solid argon, boron atoms spontaneously reacted with NO to form the insertion molecule NBO. The BNBO and OBNNO molecules were formed by the B and NO addition reactions to NBO. The linear BBNO and BBBNO nitrosyls also were formed spontaneously on annealing. These molecules photochemically rearranged to the more stable BNBO and BNBBO isomers, which have linear polyyne-like structures. The photosensitive OBNNO molecule decomposed to form the NNBO(2) van der Waals complex. In addition, the novel OBON diradical was also formed on photolysis in high-concentration NO experiments.