Naoto Ando

Comprehensive photoelectron spectroscopic study of anionic clusters of anthracene and its alkyl derivatives: Electronic structures bridging molecules to bulk

The evolution of the electronic structure of molecular aggregates is investigated using anion photoelectron (PE) spectroscopy for anionic clusters of anthracene (Ac) and its alkyl derivatives: 1-methylanthracene (1MA), 2-methylanthracene (2MA), 9-methylanthracene (9MA), 9,10-dimethylanthracene (DMA), and 2-tert-butylanthracene (2TBA). For their monomer anions (n=1), electron affinities are confined to the range from 0.47 to 0.59 eV and are well reproduced by density functional theory calculations, showing the isoelectronic character of these molecules. For cluster anions (n=2-100) of Ac and 2MA, two types of isomers I and II coexist over a wide size range: isomers I and II-1 (4< or =n<30) or isomers I and II-2 (n> or = approximately 40 for Ac and n> or = approximately 55 for 2MA). However, for the other alkyl-substituted Ac cluster anions (i.e., 1MA, 9MA, DMA, and 2TBA), only isomer I is exclusively formed, and neither isomer II-1 nor II-2 is observed. The vertical detachment energies (VDEs) of isomer I in all the anionic clusters depend almost linearly on n(-1/3). In contrast, the VDEs of isomers II-1 (n> or =14) and II-2 (n=40-100), appeared only in Ac and 2MA cluster anions, remain constant with n and are approximately 0.5 eV lower than those of isomer I. The PE spectra revealed the characteristics of each isomer: isomer I possesses a monomeric anion core that is gradually embedded into the interior of the cluster with increasing n. On the other hand, isomers II-1 and II-2 possess a multimeric (perhaps tetrameric) anion core, but they differ in the number of layers from which they are made up; monolayer (isomer II-1) and multilayers (isomer II-2) of a two-dimensionally ordered, finite herringbone-type structure, in which electron attachment produces only little geometrical rearrangement. Moreover, the agreement of the constant VDEs of isomer II-2 with the bulk data demonstrates the largely localized nature of the electronic polarization around the excess charge in a crystal-like environment, where about 50 molecules provide a charge stabilization energy comparable to the bulk.

Photoelectron spectroscopy of cluster anions of naphthalene and related aromatic hydrocarbons

The electronic structures and structural morphologies of naphthalene cluster anions, (naphthalene)(n)(-) (n=3-150), and its related aromatic cluster anions, (acenaphthene)(n)(-) (n=4-100) and (azulene)(n)(-) (n=1-100), are studied using anion photoelectron spectroscopy. For (naphthalene)(n) (-) clusters, two isomers coexist over a wide size range: isomers I and II-1 (28 < or = n < or =60) or isomers I and II-2 (n > or = ~60). Their contributions to the photoelectron spectra can be separated using an anion beam hole-burning technique. In contrast, such an isomer coexistence is not observed for (acenaphthene)(n) (-) and (azulene)(n) (-) clusters, where isomer I is exclusively formed throughout the whole size range. The vertical detachment energies (VDEs) of isomer I (7 < or = n < or = 100) in all the anionic clusters depend linearly on n(-13) and their size-dependent energetics are quite similar to one another. On the other hand, the VDEs of isomers II-1 and II-2 produced in (naphthalene)(n)(-) clusters with n > or = approximately 30 remain constant at 0.84 and 0.99 eV, respectively, 0.4-0.6 eV lower than those of isomer I. Based upon the ion source condition dependence and the hole-burning photoelectron spectra experiments for each isomer, the energetics and characteristics of isomers I, II-1, and II-2 are discussed: isomer I is an internalized anion state accompanied by a large change in its cluster geometry after electron attachment, while isomers II-1 and II-2 are crystal-like states with little structural relaxation. The nonappearance of isomers II-1 and II-2 for (acenaphthene)(n)(-) and (azulene)(n)(-) and a comparison with other aromatic cluster anions indicate that a highly anisotropic and symmetric pi-conjugated molecular framework, such as found in the linear oligoacenes, is an essential factor for the formation of the crystal-like ordered forms (isomers II-1 and II-2). On the other hand, lowering the molecular symmetry makes their production unfavorable.

Negative ion photoelectron spectroscopy of acridine molecular anion and its monohydrate

Negative ion photoelectron spectroscopy was employed to investigate the electronic structure of the acridine molecular anion and its monohydrated anion in the gas phase. Their adiabatic electron affinities were measured to be 0.896+/-0.010 and 1.18+/-0.05 eV, and the low-lying electronic excited states in both neutral acridine and in its monohydrate were revealed. The photoelectron spectra clearly exhibit the presence of low-lying singlet and triplet states having a (pi,pi*) configuration in an uncomplexed acridine molecule. Comparison of the photoelectron spectrum of acridine with that of anthracene shows that photodetachment processes into the excited states of (n,pi*) configuration have little intensity, implying a relatively large intramolecular structural relaxation in the (n,pi*) states.

Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions: the effect of molecular shape on molecular assembly and ion core character.

Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions, (o-TP)n(-) (n = 2-100), (m-TP)n(-) (n = 2-100), and (p-TP)n(-) (n = 1-100), respectively, are conducted to investigate the effect of molecular shape on the molecular aggregation form and the resultant ion core character of the clusters. For (o-TP)n(-) and (m-TP)n(-), neither magic numbers nor discernible isomers are observed throughout the size range. Furthermore, their vertical detachment energies (VDEs) increase up to large n and depend linearly on n(-1/3), implying that they possess a three-dimensional (3D), highly reorganized structure encompassing a monomeric anion core. For (p-TP)n(-), in contrast, prominent magic numbers of n = 5, 7, 10, 12, and 14 are observed, and the VDEs show pronounced irregular shifts below n = 10, while they remain constant above n = 14 (isomer A). These results can be rationalized with two-dimensional (2D) orderings of p-TP molecules and different types of 2D shell closure at n = 7 and 14, the monomeric and multimeric anion core, respectively. Above n = 16, the new feature (isomer B) starts to appear at the higher binding side of isomer A, and it becomes dominant with n, while isomer A gradually disappears for larger sizes. In contrast to isomer A, the VDEs of isomer B continuously increase with the cluster size. This characteristic size evolution suggests that the transition to modified 2D aggregation forms from 2D ones occurs at around n = 20.