Lexical conditions on syntactic knowledge: auxiliary selection in native and non-native grammars of Italian

The theoretical focus is on the linguistic intuitions of native and non-native speakers of Italian about a number of grammatical phenomena related to the choice between the auxiliaries ESSERE ('be') and AVERE ('have') with non-transitive (unaccusative and unergative) verbs. It is argued that a purely syntactic account of unaccusativity is insufficient to capture the variation exhibited by these verbs. In particular, it is claimed that the unmarked selection of ESSERE with unaccusatives and of AVERE with unergatives in the present perfect tense is sensitive not only to a hierarchy of syntactic configurations (as assumed by the Government-Binding version of the Unaccusativity Hypothesis) but also to lexical hierarchies that subdivide the range of unaccusative and unergative verbs along semantic dimensions. Such hierarchies distinguish 'core', or prototypical, types of verbs from peripheral ones , and are consistent with the historical evolution of auxiliaries in Romance. However, auxiliary selection in syntactically marked 'restructuring' constructions, induced by certain Raising and Control verbs, is not sensitive to these semantic dimensions. It was predicted that the interaction between syntactic and semantic constraints would give rise to systematic variability in native speakers' linguistic intuitions, manifested in consistent and determinate acceptability judgments on core types of verbs, and variable or indeterminate judgments on peripheral types of verbs. It was also predicted that non-natives would differ from natives in terms of the extent to which indeterminate judgments penetrated from the periphery to the core.Methodologically, this study represents the first application of magnitude estimation techniques to the elicitation of linguistic acceptability judgments. Magnitude estimation makes it possible to measure variability in acceptability judgments directly, which has the advantage of producing interval scales that can then be properly analysed by parametric statistics. Other ranking elicitation procedures produce only ordinal measurements. A systematic comparison between the judgments obtained by means of magnitude estimation and those obtained by means of a cardsorting ranking procedure indicates that both native and non-native speakers are able to judge acceptability via magnitude estimation with at least as much delicacy as via card-sorting. In some cases, magnitude estimation produces finer-grained distinctions of unacceptability, and reveals differences between native and near-natives which are not reproduced in the card-sorting task.A series of experiments was conducted addressing the three issues of (a) variability in native intuitions, (b) progressive development of non-native knowledge, and (c) ultimate attainment at near-native competence levels. Acceptability judgments were collected from Italian native speakers and English-speaking learners of Italian at four proficiency levels (beginner, intermediate, advanced, near-native). A group of French near-native speakers of Italian was also tested for the purpose of comparison with the English near-natives.Tnis study has both a theoretical and a methodological dimension. Theoretically, it is concerned with variation and indeterminacy in linguistic acceptability judgments. Methodologically, it involves the application of a rigorous procedure for the elicitation of judgment data that is sensitive to informants' variable or indeterminate intuitions.The results show that (a) the judgments of native Italians are sensitive to different lexical-semantic hierarchies of unaccusative and unergative verbs: judgments on the basic syntactic reflexes of the unergative/unaccusative distinction (auxiliary selection and ne-cliticization) exhibit more or less determinacy depending on the semantic characterization of individual verbs: however, native speakers discriminate categorically between possible and impossible, obligatory and optional auxiliary change under restructuring, irrespective of the semantics of the inducing verb; (b) nonnative judgments reflect a difference in learnability between lexical-semantic and purely syntactic distinctions. Lexical-semantic hierarchies affect the development and ultimate shape of non-native grammars, in that interlanguage representations for core lexical classes are constructed earlier than those for peripheral classes, with non-native acceptability values gradually approximating the native values. Peripheral restructuring constructions, however, never become determinate in the interlanguage grammars of English learners, which are incomplete in this respect even at the nearnative level. In contrast, French near-native speakers of Italian show evidence of having constructed determinate, but divergent representations of these syntactic phenomena. It is argued that such differences in ultimate attainment reflect differences in the overall representations of unaccusativity in French and English

Investigations of Metal/Organic Interfaces and Metalation Reactions of Organic Semiconductors

Modern electronic devices are increasingly based on organic semiconductors. The performance of such devices crucially depends on the properties of the interface between the organic semiconductors and the metal contacts. Understanding the influence of the topology of the organic semiconductor’s conjugated pi-electron system on the interface interaction could greatly improve the device’s performance. Furthermore, the knowledge about reactions of heteroatomic organic semiconductors with metal atoms during electrode fabrication may lead to enhanced lifetimes of such devices. This cumulative dissertation comprises several publications and a number of so far unpublished results, addressing metal/organic interface interactions and metalation reactions of heteroatomic organic semiconductors. The properties of the interfaces are tailored by investigating the alternant aromatic molecules naphthalene and pyrene as well as the nonalternant aromatic molecules azulene and azupyrene on different metallic singlecrystal surfaces. Investigations by means of temperature-programmed desorption reveal stronger desorption energies for the non-alternant molecules on both Ag(111) and Cu(111). The biggest difference is observed on Cu(111), on which azulene and azupyrene are chemisorbed, whereas naphthalene and pyrene are physisorbed. The enhanced interface interaction of the non-alternant molecules is associated with the formation of surface dipoles that lead to stronger intermolecular repulsion between the adsorbed molecules. These results are supported by additional surface science methods, such as X-ray photoelectron spectroscopy or near-edge X-ray absorption fine structure spectroscopy, as well as density functional theory calculations conducted by group members and external collaboration partners. Detailed quantitative analysis of temperature-programmed desorption data of benzene on Cu(111) and Ag(111) yields experimental desorption energies that can be used as a benchmark for theoretical adsorption energies derived by density functional theory calculations. The interactions of metal/organic interfaces are compared with organic/inorganic interfaces in the case of pentacene and its fluorinated derivative perfluoropentacene on Au(111) as well as on bulk and two-dimensional MoS2 in a collaboration project. Organic semiconductors often interact weakly with inorganic surfaces, e.g., the thermal desorption of the first molecular layer is indistinguishable from multilayer desorption. No monolayer desorption peaks are observed as is mostly the case on metal surfaces. However, monolayer desorption of pentacene and perfluoropentacene on MoS2 occurs at significantly higher temperatures than the multilayer desorption. Detailed analysis reveals that the monolayers of both molecules are entropically stabilized. Codeposition of both molecules results in strong attractive intermolecular interactions on MoS2, while these interactions are weaker on Au(111). Metalation reactions of organic semiconductors with metal atoms, e.g., Co on tetraphenylporphyrin and Ca on alpha-sexithiophene, during interface preparation were investigated by means of hard X-ray photoelectron spectroscopy and temperature-programmed desorption mass spectrometry. The thickness of the reaction zone is changed by variation of experimental properties during interface formation. It is found that only the sample temperature during metal atom deposition and the metal atom flux in the case of Ca have an impact on the reaction depth, which is usually limited to few nanometers. In contrast to Co and Ca, Li atoms readily diffuse into the organic bulk and react with tetraphenylporphyrin over several tens of nanometers, forming dilithium tetraphenylporphyrin or monolithium monohydrogen tetraphenylporphyrin depending on the deposited Li amount. Furthermore, the transmetalation reaction of lead(II) tetraphenylporphyrin with Cu atoms on the Cu(111) surface was proven by temperature-programmed desorption. In addition, the Ullmann coupling reaction of bromo- and iodobenzene on Cu(111) was examined. While bromobenzene molecules desorb intact from the Cu(111) surface, iodobenzene molecules dissociate into iodine atoms and phenyl radicals. The latter form biphenyl that desorbs in three distinct desorption peaks at different temperatures. In a collaborative project, the oxidation state and electronic structure of Pb atoms in the newly synthesized Pb3F8 were studied by hard X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy giving evidence for the presence of Pb(II) and Pb(IV) species. The experimental results are complemented by constructional work to improve the temperatureprogrammed desorption setup. Moreover, two Igor Pro 8 scripts were written to quickly import data from different experimental setups and speed up the data treatment

Alternating ditransitives in English: a corpus-based study

This thesis is a large-scale investigation of ditransitive constructions and their alternants in English. Typically both constructions involve three participants: participant A transfers an element B to participant C. A speaker can linguistically encode this type of situation in one of two ways: by using either a double object construction or a prepositional paraphrase. This study examines this syntactic choice in the British component of the International Corpus of English (ICE-GB), a fully tagged and parsed corpus incorporating both spoken and written English. After a general introduction, chapter 2 reviews the different grammatical treatments of the constructions. Chapter 3 discusses whether indirect objects have to be considered necessary complements or optional adjuncts of the verb. I then examine the tension between rigid classification and authentic (corpus) data in order to demonstrate that the distinction between complements and adjuncts evidences gradient categorisation effects. This study has both a linguistic and a methodological angle. The overall design and methodology employed in this study are discussed in chapter 4. The thesis considers a number of variables that help predict the occurrence of each pattern. The evaluation of the variables, the determination of their significance, and the measurement of their contribution to the model involve reliance on statistical methods (but not statistical software packages). Chapters 5, 6, and 7 review pragmatic factors claimed to influence a speaker’s choice of construction, among them the information status and the syntactic ‘heaviness’ of the constituents involved. The explanatory power and coverage of these factors are experimentally tested independently against the corpus data, in order to highlight several features which only emerge after examining authentic sources. Chapter 8 posits a novel method of bringing these factors together; the resulting model predicts the dative alternation with almost 80% accuracy in ICE-GB. Conclusions are offered in chapter 9

Computational prediction of core-level spectroscopy of metal-organic interfaces to reveal chemical interactions, bonding and behaviours.

Molecules adsorbed onto metal surfaces, especially carbon-based aromatic molecules, can provide systems that offer tunable properties and can be used in organic light-emitting diodes (OLEDs). It is important to understand the behaviour of these systems at a molecular level in order to rationally engineer interfaces with specific properties. Core-level spectroscopy can provide a beneficial method to probe aspects of molecule-metal interfaces such as geometrical structure, stability, chemical bonding and electronic structure. X-ray photoelectron spectroscopy (XPS) and near-edge absorption fine structure (NEXAFS) spectroscopy can be used in tandem to gain significant insight into the studied system. However, the resulting spectra from these techniques can often prove hard to fully analyse as they contain multiple close-lying features and loss of clarity from broadening. This is where simulations of spectra can come in to help to disentangle and interpret spectra. This thesis establishes practical simulation workflows to predict XPS and NEXAFS spectra of metal-organic interfaces based on Density Functional Theory (DFT). These methods are applied to study the adsorption of aromatic adsorbates on metal surfaces, two-dimensional networks, and an oxidised diamond surface. As part of this work, the assessment of the performance and accuracy of simulations against experiment was carried out. Core-level simulations on various systems were performed to rationalise experimental findings on structure, stability, and surface chemical bonding

Ligand Design, Coordination and Electrochemistry of Nonbenzenoid Aryl Isocyanides

Abstract In this work, the strategy for accessing planar chiral isocyanides has been developed and the first member of this family has been isolated in the optically pure form and fully characterized. 2-Methyl-substituted isocyanoferrocene can be synthesized from commercial ferrocenylcarboxylic acid and S- or R-forms of valinol. Both pS and pR forms of this new organometallic isocyanide were isolated in excellent percent enantiomeric excess. The unambiguous assignment of the absolute configuration was obtained through the X-ray chrystallographic study of the PdI2 adduct with (pS)-1-isocyano-2-methylferrocene that contains two planar chiral isocyanoferrocene ligands bound to the PdII center in the trans fashion. Electrochemical analysis of the [Cr(CNR)6]0,1+,2+ (R = ferrocenyl and cymantrenyl) series indicated that the electronic influence of the ferrocenyl moiety within a ligand is similar to that of a hydrocarbon aryl substituent, rather than an alkyl group (e.g., methyl). In addition, this work has demonstrated that electronic (especially, the pi-acidity) tuning of the isocyanocyclopentadienide ligand can be accomplished within a substantial range by changing the nature of the transition metal fragment bound to its ring. A systematic electrochemical investigation of the first isocyanoazulene ligands and their electron-rich complexes has been accomplished. The electronic properties of azulene and its isocyanide derivatives have been investigated by electronic spectroscopy, cyclic voltammetry, and theoretical calculations. Through this work, the properties of the Frontier molecular orbitals of isocyanoazulenes were determined quantitatively. The previous qualitative theory predicting the effect of substituents on the magnitude of azulene's HOMO-LUMO gap (and, hence, its optical properties) popularized by Liu et al.81 does not hold in the case of the isocyanide substituent. The unexpected directions of the shifts of the S0 → S1 transition for 1- and 2-isocyanoazulenes have been fully rationalized by considering together the electronic spectra, electrochemical properties, and the time-dependant density functional theory structures of these species. Furthermore, the first comprehensive quantitative electrochemical assessment of electronic inhomogeneity of the azulenic scaffold has been perfomed by analyzing the redox properties of the complexes Cr(CNxAz)6 (Az = azulenyl' x = 1, 2, 4, 5, 6). The quantitative series of the donor/acceptor ratios of the isocyanoazulene ligands has been obtained. The first large gold macrocycle incorporating the redox-active ferrocene unit has been isolated and fully characterized. The 1,1'-diisocyanoferrocene ligand employed in this study undergoes eta-2 coordination to a pair of AuI ions under thermodynamic control, i.e., no oligomeric structures are produced at all. Formation of the cyclic product is facilitated by the near perfect match between the interplanar distance involving the five-membered rings of the diisocyanoferrocene ligand and the AuAu separation within the di-gold precursor that features an aurophilic interaction. Overall, the "parent" motifs to be incorporated in the potential novel mesogenic materials containing both ferrocene and azulene units have been established and the reasons for challenges in isolating gold(I) complexes with mixed isocyanide ligands have been uncovered

On looking into words (and beyond): Structures, Relations, Analyses

On Looking into Words is a wide-ranging volume spanning current research into word structure and morphology, with a focus on historical linguistics and linguistic theory. The papers are offered as a tribute to Stephen R. Anderson, the Dorothy R. Diebold Professor of Linguistics at Yale, who is retiring at the end of the 2016-2017 academic year. The contributors are friends, colleagues, and former students of Professor Anderson, all important contributors to linguistics in their own right. As is typical for such volumes, the contributions span a variety of topics relating to the interests of the honorand. In this case, the central contributions that Anderson has made to so many areas of linguistics and cognitive science, drawing on synchronic and diachronic phenomena in diverse linguistic systems, are represented through the papers in the volume. The 26 papers that constitute this volume are unified by their discussion of the interplay between synchrony and diachrony, theory and empirical results, and the role of diachronic evidence in understanding the nature of language. Central concerns of the volume include morphological gaps, learnability, increases and declines in productivity, and the interaction of different components of the grammar. The papers deal with a range of linked synchronic and diachronic topics in phonology, morphology, and syntax (in particular, cliticization), and their implications for linguistic theory