Low temperature electron transfer in strongly condensed phase

Electron transfer coupled to a collective vibronic degree of freedom is studied in strongly condensed phase and at lower temperatures where quantum fluctuations are essential. Based on an exact representation of the reduced density matrix of the electronic+reaction coordinate compound in terms of path integrals, recent findings on the overdamped limit in quantum dissipative systems are employed. This allows to give for the first time a consistent generalization of the well-known Zusman equations to the quantum domain. Detailed conditions for the range of validity are specified. Using the Wigner transform these results are also extended to the quantum dynamics in full phase space. As an important application electronic transfer rates are derived that comprise adiabatic and nonadiabatic processes in the low temperature regime including nuclear tunneling. Accurate agreement with precise quantum Monte Carlo data is observed.Comment: 16 pages, 6 figures, revised version with minor change

Trigonal-bipyramidal vs. octahedral coordination in indium(III) complexes with potentially S,N,S‐tridentate thiosemicarbazones

Three bis‐chelates of indium(III) with (partially fluorinated) S,N,S‐tridentate thiosemicarbazones (H2L) were prepared and their structures were studied in solution and in the solid state by NMR, ESI MS and single‐crystal X‐ray diffraction. The three compounds are isostructural in solution with five‐coordinate InIII ions and two differently coordinated thiosemicarbazonato ligands, [In(L)(HL)]. A temperature‐dependent 1H NMR study reflects the presence of dynamic processes in the molecules such as the resolution of hindered rotation around CN bonds with partial double‐bond character and the pH‐triggered isomerization between 5‐ and 6‐coordinate species. The latter is confirmed by the isolation of compounds with different solid‐state structures, [In(L)(HL)] and [In(L)2]–, depending on fluorine‐substitutions in the periphery of the thiosemicarbazones

A new xantphos-type ligand and its gold(I) complexes: Synthesis, structure, luminescence

A novel xantphos analog diphosphine ligand, 9,9-dimethyl-4,5-bis(diphenylphosphinomethyl)-9H-xanthene (X(CP)2), with methylene groups inserted between the xanthene skeleton and the two diphenylphosphine units, has been synthesized. A two-coordinate and a three-coordinate gold(I) complex of the ligand, [Au2Cl2(X(CP)2)] and [AuCl(X(CP)2)], have been prepared and studied by X-ray diffraction, NMR and optical spectroscopy. In the solid state, [AuCl(X(CP)2)] adopts a highly ordered structure with a planar xanthene skeleton that faces another plane composed of two phenyl rings and the AuCl moiety. The structure of [Au2Cl2(X(CP)2)] is much less regular, the two P–Au–Cl vectors point to the opposite sides of the folded xanthene backbone. The exchange-broadened resonances in the NMR spectra of [AuCl(X(CP)2))] indicate that this complex exists as a mixture of various chemical species and/or conformers in solution. In contrast, the NMR spectra of [Au2Cl2(X(CP)2)] exclude any medium-range exchange processes. Aurophilic interactions are absent in both X(CP)2 complexes. X(CP)2, as well as its two gold complexes, is phosphorescent in the solid state; the complexes emit at higher wavelengths and with longer lifetimes than the free ligand

Ontology-based Prediction of Compound Relations : A Study Based on SUMO

This paper explores the interaction between conceptual structure and morpho-syntax. In particular, we show that ontology-based conceptual classification can be used to predict internal relations in compounds. We propose an ontology-based approach to predict the semantic relation between the two component words in Mandarin VV compounds. A Mandarin VV compound is classified according to the eventive relation between the two simplex verbs. These relations specify how the eventive meanings of the two simplex verbs combine to form the meaning of the compound. The three types of eventive relations that we deal with in this paper are: coordinate, modificational, and resultative. Since the way in which two events combine with each other depends upon their event types, we hypothesize that the eventive relations can be predicted by the conceptual classified event types of the two simplex verbs. An approach of ontology-based prediction is proposed based on this hypothesis. The assignment of ontology classification for each simplex verb is based on SUMO and Sinica BOW. The correlation between the ontology class of each verb position and each eventive type is trained and scored based on a manually tagged lexical database. We encode the ontology information of each VV compound in a 3-tuple based on these correlation scores. This 3-tuple is represented as a three-dimensional vector and used to predict the eventive type of new VV compounds. Our classification experiment on unknown VV compounds yields good recall and precision

Compound formation principles in Livonian

Compounding is one of the most productive types of Livonian word formation. Compounds typically are synthetic and contain one or more modifiers, which follow the head of the compound. Most compound nouns have a singular genitive modifier. Livonian also has an important sub-group of compound nouns and adjectives, which has preserved the historical singular genitive ending *-n in modifiers. On rare occasions, the modifier can also be nominative. In such compounds, the modifier partially agrees in case with the head. An important group of Livonian compound nouns, created on the Latvian model, has declinable active present participles as modifiers. The Livonian system of compounds, just like Livonian itself, generally follows traditional Finnic compound word formation principles, but also has characteristics of compound formation typical of Latvian. Understanding the Livonian system of compounds was greatly helped by use of the Livonian written language corpus.Kokkuvõte. Valts Ernštreits: Liitsõnade moodustamise põhimõtted liivi keeles. Liitmine on üks produktiivsemaid liivi keele sõnamoodustuse liike. Üldjuhul on liitsõnad sünteetilised, koosnevad ühest või mitmest täiendsõnast, millele järgneb põhisõna. Enamiku liitsõnadest moodustavad liitnoomenid, milles täiendsõna on valdavalt ainsuse genitiivis. Liivi keeles esineb ka oluline liitsubstantiivide ja -adjektiivide rühm, mis on säilitanud täiendsõnas ajaloolise ainsuse genitiivi lõpu *-n. Harvadel juhtudel saab liitsubstantiivides täiendsõna olla ka nominatiivis ning sellistes liitsõnades ühildub täiendsõna käänamisel osaliselt põhisõnaga. Läti keele eeskujul on liivi keeles tekkinud oluline liitnoomenite rühm, mille täiendsõnana kasutatakse tegevust tähistavat käänduvat aktiivi oleviku partitsiipi. Nii võib öelda, et liivi liitsõnasüsteemis nagu ka liivi keeles üldisemalt ilmnevad nii läänemeresoome keelte traditsioonilised liitsõnade moodustuspõhimõtted kui ka läti keelele iseloomulikud liitsõnade moodustamise jooned. Liivi keele liitsõnade süsteemist ülevaate tegemist aitas oluliselt liivi kirjakeele korpuse kasutamine.Märksõnad: liitsõnad, keeleajalugu, keelekontaktid, liivi keelKubbõvõttõks. Valts Ernštreits: Ītsõnād sǟdimiz pūojmõtkõd līvõ kīels. Ītimi um ikš amā produktīvist līvõ kīel sõnādlūomiz vīțist. Ītsõnād amā jemīņ ātõ sintētizt, nēḑi vīțõb ikš agā setmiņ līekõsõnnõ, mis tagān um alīzsõnā. Amā jemīņ līvõkīels ātõ nǟdõb ītnomend, kus līekõsõnā um īdlug genitīvs. Līvõ kīelst um lieudtõb ka tǟdzi ītsubstantīvõd ja ītadjektīvõd grup, kus līekõsõnā um vȯidõn vanā genitīv lopāndõks *-n. Ōrastiz ītsubstantīvis līekõsõnā võib vȱlda ka nominatīvs ja seļļižis ītsõņši līekõsõnā ītõb nõtkīs alīzsõnāks. Lețkīel nägțõb pierrõ līvõ kīels um suggõn tǟdzi ītnomenõd grup, kus līekõsõnā um nõtkiji partitsip. Võib kītõ, ku līvõ kīel ītsõnād sistēms nemē ka līvõ kīels amnämniz ātõ lieudtõb nei vāldamiersūomõ kīeld irdizt ītsõnād lūomiz pūojmõtkõd, ku ka lețkīel ītsõnād lūomiz irdõkst. Līvõ kīel ītsõnād sistēmõ um dižānist äbțõn mȯistõ līvõ kērakīel korpus kȭlbatimi

Morphosyntactic Interleaving in Vietnamese and Pacoh

Interleaving, a surface configuration in some languages in which the parts of two adjacent words are interspersed with each other, has been argued to be a phonological phenomenon. In this paper, I investigate interleaving in Vietnamese and a related language, Pacoh (Katuic, Mon-Khmer), and argue that it is the result of morphosyntactic operations and structures and not a phonological operation. I present three pieces of evidence that interleaving is morphosyntactic in nature: (i) interleaving cannot apply to all syllables, only those in certain morphosyntactic environments; (ii) interleaving manipulates polysyllabic units and can apply to 3-part compounds, showing that it is manipulating morphosyntactic structure and not phonological structure; and (iii) interleaving creates extra syntactic-semantic force, suggesting a change in the syntax. I propose an analysis in which interleaving is the result of the structure of coordinate compounds, whose members have no precedence relation with each other, in combination with an alternate traversal of the syntactic tree during linearization

Organisation and Contents of Korean Pedagogical Grammar - With focus on Korean: A Comprehensive Grammar (Yeon & Brown)

This paper aims to discuss how Korean pedagogical grammar should be written in terms of organisation and description of content. The arguments in this paper will be presented in practical and empirical manners rather than theoretical ones. The problematic questions and empirical issues presented arose while the author was writing a pedagogical grammar book entitled ‘Korean: A Comprehensive Grammar’, published by Routledge in early 2011. The point about pedagogical grammar is that it is not the same as linguistic grammar because they have different functions and uses. Pedagogical grammar typically requires rules that are definite, coherent, consistent,non-technical,cumulative and heuristic. Actual problems and topics at issue are discussed in the paper and the book’s table of contents is presented at the end of the paper

THE DESIGN AND SYNTHESIS OF NOVEL CHELATES FOR THE PRECIPITATION OF MERCURY

Mercury has been an element of great industrial importance since early times.This wide utilization of the element has led to pervasive mercury contamination in theglobal environment. Due to mercury\u27s high toxicity, this is a matter of great concern. Anumber of methods, includ ing phytoremediation, filtration, and precipitation/chelation,have been investigated to remove mercury from the environment. Unfortunately, thesemethods are not entirely satisfactory for the in-situ remediation of mercury from aqueousenvironments.The hypothesis of this dissertation is that this can best be accomplished by theaddition of a large and flexible sulfur-based chelate, that will bind mercury in atetracoordinate and presumably tetrahedral environment, to mercury-contaminatedwaters. Although this proved difficult due to the tendency of these ligands to decomposeinto smaller, sulfur-containing rings, the synthesis and characterization of such a chelatewas achieved. Several potential mercury-binding ligands were eventually synthesizedsignificant amounts of mercury (91-100%) from the contaminated solutions, in one caselowering the mercury levels in the water to below the CVAF detection limits. Theresulting solids lost little (andlt;15 ppb) of their mercury during leaching studies.This work demonstrates the use of tetradentate chelates in precipating Hg2+ fromwater to produce stable mercury- ligand precipitates. A calculation for the quantification ofthe geometry of a four-coordinate compound was also developed and applied to aluminum,gallium, and mercury compounds. This calculation could also be applied to the mercurycompounds described in this thesis once X-ray structures become availabl