Relations among several nuclear and electronic density functional reactivity indexes

A set of connections among several nuclear and electronic indexes of reactivity in the framework of the conceptual Density Functional Theory by using an expansion ofthe energy functional in terms of the total number of electrons and the normal coordinates within a canonical ensemble was derived. The relations obtained provided explicit links between important quantities related to the chemical reactivity of a system. This paper particularly demonstrates that the derivative of the electronic energy with respect to the external potential of a system in its equilibrium geometry was equal to the negative of the nuclear repulsion derivative with respect to the external potential

Electronic couplings and on-site energies for hole transfer in DNA: systematic quantum mechanical/molecular dynamic study

The electron hole transfer (HT) properties of DNA are substantially affected by thermal fluctuations of the π stack structure. Depending on the mutual position of neighboring nucleobases, electronic coupling V may change by several orders of magnitude. In the present paper, we report the results of systematic QM/molecular dynamic (MD) calculations of the electronic couplings and on-site energies for the hole transfer. Based on 15 ns MD trajectories for several DNA oligomers, we calculate the average coupling squares 〈 V2 〉 and the energies of basepair triplets X G+ Y and X A+ Y, where X, Y=G, A, T, and C. For each of the 32 systems, 15 000 conformations separated by 1 ps are considered. The three-state generalized Mulliken-Hush method is used to derive electronic couplings for HT between neighboring basepairs. The adiabatic energies and dipole moment matrix elements are computed within the INDO/S method. We compare the rms values of V with the couplings estimated for the idealized B -DNA structure and show that in several important cases the couplings calculated for the idealized B -DNA structure are considerably underestimated. The rms values for intrastrand couplings G-G, A-A, G-A, and A-G are found to be similar, ∼0.07 eV, while the interstrand couplings are quite different. The energies of hole states G+ and A+ in the stack depend on the nature of the neighboring pairs. The X G+ Y are by 0.5 eV more stable than X A+ Y. The thermal fluctuations of the DNA structure facilitate the HT process from guanine to adenine. The tabulated couplings and on-site energies can be used as reference parameters in theoretical and computational studies of HT processes in DNA

Estimation of electronic coupling in π -stacked donor-bridge-acceptor systems: correction of the two-state model

Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of Vda because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a π stack, where donor and acceptor are separated by a bridging unit, can be obtained as Ṽ da = (E2 - E1) μ12 Rda + (2 E3 - E1 - E2) 2 μ13 μ23 Rda2, where E1, E2, and E3 are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, μij is the transition dipole moments between the states i and j, and Rda is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement (within 5%) with the data of the three-state generalized Mulliken-Hush model

Estimates of electronic coupling for excess electron transfer in DNA

Electronic coupling Vda is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of Vda for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a π stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of Vda are obtained with the standard 6-31 G* and extended 6-31++ G* basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of Vda are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements Vda for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack

Electronic and vibrational contributions to first hyperpolarizability of donor-acceptor-substituted azobenzene

In this study we report on the electronic and vibrational (hyper)polarizabilities of donor–acceptorsubstituted azobenzene. It is observed that both electronic and vibrational contributions to the electricdipole first hyperpolarizability of investigated photoactive molecule substantially depend on the conformation. The contributions to the nuclear relaxation first hyperpolarizability are found to be quite important in the case of two considered isomers (cis and trans). Although the double-harmonic term is found to be the largest in terms of magnitude, it is shown that the total value of the nuclear relaxation contribution to vibrational first hyperpolarizability is a result of subtle interplay of higher-order contributions. As a part of the study, we also assess the performance of long-range-corrected densityfunctional theory in determining vibrational contributions to electric dipole (hyper)polarizabilities. In most cases, the applied long-range-corrected exchange correlation potentials amend the drawbacks of their conventional counterparts

Applying recommendations to aligncompetences, methodology and assessment in Telematics, Computing and Electronic Engineering courses

The alignment between competences, teaching-learning methodologies and assessment is a key element of the European Higher Education Area. This paper presents the efforts carried out by six Telematics, Computer Science and Electronic Engineering Education teachers towards achieving this alignment in their subjects. In a joint work with pedagogues, a set of recommended actions were identified. A selection of these actions were applied and evaluated in the six subjects. The cross-analysis of the results indicate that the actions allow students to better understand the methodologies and assessment planned for the subjects, facilitate (self-) regulation and increase students’ involvement in the subjects.

La gestió dels llibres electrònics a la Biblioteca virtual de la UOC

El text que es presenta mostra com es du a terme la gestió dels llibres electrònics a la Biblioteca virtual (d'ara endavant BV) de la Universitat Oberta de Catalunya (d'ara endavant UOC). La BV posa un èmfasi especial en l'adquisició de llibres digitals per millorar l'accés als usuaris als recursos i col¿leccions d'una universitat que es caracteritza per la virtualitat. El document presenta, en primer lloc, l'entorn en què s'adquireixen i s'utilitzen els llibres electrònics: s'expliquen els diferents escenaris d'adquisició en els quals es pot trobar la biblioteca i es defineixen els circuits interns que en permeten la gestió i els processos tècnics dels documents. A continuació es mostren les diferents opcions d'accés i consulta de llibres electrònics que actualment s'ofereixen des de la biblioteca i s'expliquen les anàlisis d'usos d'aquests documents. Finalment es presenten les conclusions a les quals arriba la BV sobre el nou context de llibres electrònics.

Bundling electronic journals and competition among publishers

Site licensing of e-journals has been revolutionizing the way academicinformation is distributed. However, many librarians are concerned aboutthe possibility that publishers might abuse site licensing by practicingbundling. In this paper, we analyze the private and social incentives forthe publishers to use bundling in the context of STM electronic journalmarket. In the short run in which the number of journals is exogenouslygiven, we find a strong conflict between the two incentives: each publisherfinds bundling optimal and bundling increases the industry profit butreduces social welfare. However, in the long run we find that publishersmight have higher incentives to introduce new journals under bundlingthan without bundling and, in this case, bundling can reduce the industryprofit while increasing social welfare. Finally, we examine publishers incentive to provide links to the websites of the rival publishers underbundling and show that even asymmetric publishers have incentive tointerconnect.

Electronic titling: Potential and risks

Initiatives in electronic conveyancing and registration show the potential of new technologies to transform such systems, reducing costs and enhancing legal security. However,they also incur substantial risks of transferring costs and risks among registries, conveyancersand rightholders, instead of reducing them; entrenching the private interests of conveyancers,instead of increasing competition and disintermediating them; modifying the allocation of tasksin a way that leads in the long term to the debasement of registries of rights with indefeasibletitle into mere recordings of deeds; and empowering conveyancers instead of transactors andrightholders, which increases costs and reduces security. Fulfilling the promise of newtechnologies in both costs and security requires strengthening registries incentives andempowering rightholders in their interaction with registries.

De iure et de facto: una anàlisi paleogràfica de documents notarials familiars

Treball de recerca realitzat per alumnes d’ensenyament secundari i guardonat amb un Premi CIRIT per fomentar l'esperit científic del Jovent l’any 2010. La hipòtesi amb la que s’ha treballat és que els documents antics són una font de coneixement bàsic i fiable per revelar les relacions familiars i patrimonials. S’ha realitzat un estudi paleogràfic molt acurat i rigorós de sis documents notarials (des del 1905 al 1958) relacionats amb els avantpassats de l’autora. En ells es tracten de temes diversos com capítols matrimonials, compres-vendes, inventaris, herències o repudiacions. Un cop analitzats els seus continguts, s’han desenvolupat dos arbres genealògics on s'han inclòs les informacions bàsiques extretes dels documents analitzats prèviament. S'ha completat l'estudi amb unes visites als arxius de Cervera i Igualada on ha realitzat unes entrevistes relacionades amb el seu treball. També ha visitat els llocs que s'esmenten en els documents. Amb tot el seu estudi, s'ha pogut concloure amb seguretat que la seva hipòtesi era certa: els documents antics són una font real de coneixement ja que, com ella mateixa diu, les fonts escrites revelen molt més que paraules. En aquest cas l'han servit a l'autora per conèixer aspectes diferents relacionats amb la numismàtica, les mides, la toponímia, els drets i deures de les persones i, com no, també d'antigues relacions familiars i patrimonials de la seva família.

Bases de datos XML nativas

Conèixer les diferents opcions a l'hora d'emmagatzemar dades i documents amb format XML. Familiaritzar-se amb els SGBD nadius i l'accés i maneig de la informació. Conèixer diferents formes d'accés al SGBD, conèixer les APIs disponible Centre en el llenguatge Java. Integració de tots els coneixements adquirits, desenvolupant una aplicació que accedeixi i gestioni dades emmagatzemades al SGBD.

Towards storage and access of electronic theses: A proposal of its organisation for the Consortium of Catalan Libraries

Els objectius d'aquest informe són realitzar un estudi de la tècnica en la digitalització, l'emmagatzematge i l'accés a les tesis doctorals electròniques, per tal de fer una proposta d’organització al Consorci de Biblioteques Universitàries de Catalunya (CBUC). Actualment, tot i que existeixen diverses iniciatives a Europa, és als EUA on la digitalització de tesis doctorals s’ha desenvolupat més amb la creació de la Networked Digital Library for Theses and Dissertation (NDLTD), i ha estat qui ha definit els estàndards en aquest camp. En el següent informe es planteja i es recomana al CBUC l’adhesió institucional a l’NDLTD per poder gaudir de la seva experiència.

El sistema de gestión documental de la Universitat de Barcelona en el marco de la Administración electrónica: un elemento más para fomentar la mejora continua

[eng] We describe the project for the organization of the documentary management system at the University of Barcelona, which is inspired by the opportunities presented by the introduction of electronic administration. We stress the function of the documentary management system as an agent for promoting continuous innovation and improvement. We illustrate this vision with a description of the process of introducing the documentary management system in the area of research.

Una lectura de la Llei 10/2001, de 13 de juliol, d'arxius i documents

S'analitza el procés d'elaboració de la nova Llei d'arxius destacant les principals modificacions que recull el text definitiu en relació al projecte. Es comenten també els punts més destacats de la Llei al voltant de tres eixos principals: la definició del Sistema d'Arxius de Catalunya, el sistema de gestió documental i l'accés als documents del patrimoni documental català.

Un model d'implantació d'un sistema de gestió de la documentació administrativa: el projecte DursiGED

[cat] Aquest article descriu el procés d'implantació d'un sistema de gestió de la documentació administrativa al Departament d'Universitats, Recerca i Societat de la Informació de la Generalitat de Catalunya (actualment Departament d'Innovació, Universitats i Empresa). El projecte, anomenat DursiGED, ha inclòs l'anàlisi, el desenvolupament i la implantació dels productes i serveis necessaris per gestionar la documentació electrònica i en suport paper de manera normalitzada i d'acord amb uns paràmetres de qualitat. L'article inclou la descripció de la planificació del projecte, el procés d'implantació i seguiment, i els productes i serveis que n'han resultat.