Locally C -Nash groups

This is a post-peer-review, pre-copyedit version of an article published in Revista Matemática Complutense. The final authenticated version is available online at : http://dx.doi.org/10.1007/s13163-018-0278-1We introduce the category of locally C-Nash groups, basic examples of such groups are complex algebraic groups. We prove that the latter form a full subcategory. We also show that both, abelian locally Nash and abelian locally C-Nash groups, can be characterised via meromorphic maps admitting an algebraic addition theorem; we give an invariant of such groups associated to the groups of periods of a chart at the identity. Finally, we prove that the category of simply connected abelian locally C-Nash groups coincides with that of universal coverings of the abelian complex irreducible algebraic groups (a complex version of a result of Hrushovski and Pillay in Isr J Math 85(1–3):203–262, 1994; Conflu Math 3(4):577–585, 2011)Elías Baro and Margarita Otero are partially supported by Spanish MTM2014-55565-P and Grupos UCM 910444. Juan de Vicente also supported by a grant of the International Program of Excellence in Mathematics at Universidad Autónoma de Madri

The role of the electrolyte on the SERS spectra of pyridine

SERS spectra of pyridine has been recorded on a silver electrode in a potential range from 0.0 to -1.20 V with a saline solution, pyridine / KCl (0.1M / 0.1M), by using the 514.5 nm exciting line by us [1]. Under these experimental conditions, the maximum intensity of the enhanced 8a and 9a bands is reached at -0.75 V and -1.20 V, respectively, being the 9a band what dominates the spectrum at negative electrode potential. Although this behavior has been explained under a resonant charge transfer mechanism, the nature of the electronic resonance processes involved in the enhancement of each band is different. The 8a band is enhanced due to an electronic excitation between the ground and excited charge transfer electronic state of the metal-adsorbate surface complex, while the activity of the 9a band is due to a plasmon-like excitation taking into account an overall electronic structure of small metal clusters [2] which is able to selectively modify the relative intensities of specific SERS band. We intend now to record pyridine SERS spectra under the same experimental conditions but varying only the type of electrolyte in order to check how it affects the relative intensities and vibrational wavenumbers of the bands as well as the electrode potential to which the enhanced bands reach the maximum intensity. Different electrolytes like KCl, NaCl, KBr, NaBr and Na2SO4, have been selected in such way that allows us to compare SERS spectra in which changes only the cation or the anion of the electrolyte. From the analysis of all these SERS spectra, it can be concluded that no significant wavenumbers shifts have been detected, while the relative intensities of the bands and the electrode potential to which the maximum intensity is reached are slightly modified. NaBr electrolyte requieres more negative electrode potential in order to enhance the 8a and 9a bands and to resolve the 12 and 1 pair. Acknowledgements We are grateful to the Spanish MINECO (CTQ2012-31846) and Junta de Andalucía (FQM-5156 and 6778), for financial support. References [1] J.F. Arenas, I. López Tocón, J.C. Otero, and J.I. Marcos, J. Phys. Chem. 100, 9254-9261 (1996). [2] J. Román-Pérez, I. López-Tocón, J.L. Castro, J. F. Arenas, J. Soto and J.C. Otero, Phys. Chem. Chem. Phys.17, 2326-2329 (2015).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Electrochemical SERS spectra of isonicotinic acid analyzed under a photoinduced charge-transfer mechanism

Isonicotinic (IN) acid is one of the three monocarboxilic derivatives of pyridine in which the acid group is located in para-position of the heterocyclic ring. It is a weak acid (pK2=4.86) and therefore, it is not completely ionized in neutral aqueous solutions, being the zwitterion and the anion the majority chemical species at neutral pH. In acidic solutions (pK1=1.84) the pyridinic nitrogen atom can be protonated yielding a third chemical species with positive charge [1]. In addition, IN acid shows two functional centres that can interact with the silver metallic surface such as the carboxilate group and the aromatic nitrogen atom. Therefore, the analysis of the SERS spectra of IN has been focused on identifying the chemical species adsorbed on the silver surface and its centre of interaction by considering the participation of a photoinduced charge-transfer (CT) mechanism in each particular SERS record as we have previously detected in the SERS of pyridine derivatives [2]. SERS spectra of the IN acid (5x10-3 M) have been recorded on silver at electrode potentials ranging from 0.00 up to -1.00 V and at different pH by using 0.1 M Na2SO4 aqueous solution as electrolyte. The figure shows the SERS recorded at basic pH. The experimental set up is described elsewhere and the excitation line of 514.5 nm wavelength was used. [2]. The detection of the presence of CT processes, which are similar to resonance Raman, requires to carry out quantum mechanical calculations [2].Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Fundamentals and Applications of Surface-Enhanced Raman Spectroscopy (SERS)

When a molecule is adsorbed on some metallic nanostructured surfaces such as silver, copper or gold, it can undergo an enormous enhancement of the Raman signal giving rise to the so called Surface-Enhanced Raman Scattering (SERS). The high sensitivity of this effect allows an accurate structural study of adsorbates at very low concentrations. The SERS effect has historically been associated with the substrate roughness on two characteristic length scales. Surface roughness on the 10 to 100 nm length scale supports localized plasmon resonances which are considered as the dominant enhancement mechanism of SERS (Electromagnetic Enhancement Mechanism: SERS-EM). It is usually accepted that these electromagnetic resonances can increase the scattered intensity by an average factor of ca. 104 to 107. A secondary mechanism often thought to require atomic scale roughness is referred to as Charge Transfer (CT) Enhancement Mechanism (SERS-CT). This mechanism involves the photoinduced transfer of an electron from the metal to the adsorbate or vice versa and involves new electronic excited CT states which result from adsorbate–substrate chemical interactions. It is also estimated that such SERS-CT mechanism can enhance the scattering cross-section by a factor of ca. 10 to 102. These two mechanisms can operate simultaneously, depending on the particular systems and experimental conditions, making difficult to recognize each one and to estimate their relative magnitude in a particular spectrum.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

An MS-CASPT2 Study of the Photodecomposition of 4- Methoxyphenyl Azide. Role of Internal Conversion and Intersystem Crossing

Aryl azides photochemistry is strongly dependent on the substituent relative position, as has been studied by time resolved resonant Raman (TR3) spectroscopy for 4-methoxyphenyl azide and its isomer 3-methoxyphenyl azide. When irradiated at 266 nm, the former results in 4,4’-dimethoxyazobenzene whereas the latter forms 1,2-didehydroazepine. It is proposed that the key step of the reactions is the formation of a nitrene derivative. Recently, it has been proposed by us that nitrenes might have a relevant role in the Surface-Enhanced Raman Scattering (SERS) of p-aminothiophenol, however, the molecular mechanism is not well known in neither of these cases. Therefore, we studied the photodecomposition of 4-methoxyphenyl azide using multiconfigurational self-consistent field methods (MC-SCF) with the CAS-SCF and MS-CASPT2 approximations and calculated the resonant Raman spectra of the relevant species using a multi-state version of Albrecht’s vibronic theory. The results propose that the reaction follows a two steps sequence after irradiation at 266 nm: an intersystem crossing 21A’/23A’’ which decays through a 21A’/21A’’ conical intersection producing molecular nitrogen and triplet 4-methoxyphenyl nitrene in its ground state.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

SERS study of different species of p-aminothiophenol adsorbed on silver nanoparticles

In the present work we have focused the discussion on the experimental and theoretical SERS spectra of the organic compound pATP recorded on silver colloids. The huge SERS of pATP on metal substrates is significantly different from its ordinary Raman spectra due to the formation of a new specie namely p,p’ –dimercaptoazobenzene (DMAB). The features of the SERS spectra of pATP are strongly dependent on many factors as i.e. the laser power density or the laser wavelength but there are still important aspects to understand as, for example, the effect of the concentration that has already been studied before by our group. In this case we have analyzed the effect of the concentration at different wavelengths on the SERS spectra of pATP on silver nanoparticles.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech