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J Mol Model ; 20(4): 2163, 2014 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-24633770


A novel mechanism for switching a molecular junction based on a proton transfer reaction triggered by an external electrostatic field is proposed. As a specific example to demonstrate the feasibility of the mechanism, the tautomers [2,5-(4-hydroxypyridine)] and {2,5-[4(1H)-pyridone]} are considered. Employing a combination of first-principles electronic structure calculations and Landauer transport theory, we show that both tautomers exhibit very different conductance properties and realize the "on" and "off" states of a molecular switch. Moreover, we provide a proof of principle that both forms can be reversibly converted into each other using an external electrostatic field.

Elétrons , Modelos Teóricos , Prótons
J Phys Chem Lett ; 3(3): 436-40, 2012 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-26285863


Femtosecond charge-transfer dynamics in self-assembled monolayers of cyano-terminated ethane-thiolate on gold substrates was investigated with the core hole clock method. By exploiting symmetry selection rules rather than energetic selection, electrons from the nitrogen K-shell are state-selectively excited into the two symmetry-split π* orbitals of the cyano end group with X-ray photons of well-defined polarization. The charge-transfer times from these temporarily occupied orbitals to the metal substrate differ significantly. Theoretical calculations show that these two π* orbitals extend differently onto the alkane backbone and the anchoring sulfur atom, thus causing the observed dependence of the electron-transfer dynamics on the symmetry of the orbital.

Chemphyschem ; 11(2): 480-8, 2010 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-20069622


The experimental ultrafast photophysics of thioxanthone in several aprotic organic solvents at room temperature is presented, measured using femtosecond transient absorption together with high-level ab initio CASPT2 calculations of the singlet- and triplet-state manifolds in the gas phase, including computed state minima and conical intersections, transition energies, oscillator strengths, and spin-orbit coupling terms. The initially populated singlet pi pi* state is shown to decay through internal conversion and intersystem crossing processes via intermediate n pi* singlet and triplet states, respectively. Two easily accessible conical intersections explain the favorable internal conversion rates and low fluorescence quantum yields in nonpolar media. The presence of a singlet-triplet crossing near the singlet pi pi* minimum and the large spin-orbit coupling terms also rationalize the high intersystem crossing rates. A phenomenological kinetic scheme is proposed that accounts for the decrease in internal conversion and intersystem crossing (i.e. the very large experimental crescendo of the fluorescence quantum yield) with the increase of solvent polarity.

J Chem Phys ; 124(9): 94310, 2006 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-16526860


Exceptionally large two-photon absorption cross sections at the infrared region have been revealed by time-dependent density functional theory calculations for asymmetric charge-transfer conjugated zinc-porphyrin derivatives. The largest two-photon cross section is found to be more than one order of magnitude larger than for the conventional two-photon active organic molecules. The calculations show that the formation of strong charge-transfer states depends on the length of the conjugation bridge between the zinc-porphyrin core and the electron donor/acceptor. The two-photon absorption cross section can be greatly enhanced by increasing the strengths of the electron donor/acceptor.

Metaloporfirinas/química , Elétrons , Fótons , Espectrofotometria Infravermelho
J Chem Phys ; 122(9): 096101, 2005 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-15836187


A series of charge-transfer Zn-porphyrin derivatives with large two-photon absorption cross sections at 1.3-1.5 microm fundamental wavelengths are designed using time-dependent hybrid density functional theory. The fluorescence of these chromospheres is expected to be in the region of 700-900 nm. These unique features make them suitable for a variety of biophotonic and telecommunication applications.

Metaloporfirinas/química , Metaloporfirinas/efeitos da radiação , Modelos Químicos , Modelos Moleculares , Fotoquímica/métodos , Absorção , Simulação por Computador , Luz , Fótons , Conformação Proteica/efeitos da radiação , Doses de Radiação , Eletricidade Estática
J Chem Phys ; 121(1): 157-61, 2004 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-15260533


The permanent dipole moment of para-amino benzoic acid has been calculated at various theoretical levels, including Hartree-Fock, second-order Møller-Plesset perturbation (MP2), coupled cluster singles and doubles (CCSD), and triples corrections CCSD(T), and hybrid density functional theory at B3LYP level. It is found that the B3LYP method fails to provide correct results for the geometry and the permanent dipole moment. These results are significantly improved by MP2 calculations. Our best estimated dipole moments obtained at CCSD and CCSD(T) levels are in good agreement with experiment.