Two-colour pulsed Raman studies of the lowest excited singlet state of tetraphenylporphyrin: band assignments and electronic structure

The resonance Raman spectra of the lowest lying singlet (S-1) state of free-base tetraphenylporphyrin and seven of its isotopomers were recorded under pump-and-probe conditions with a time delay of -2 ns between pump and probe laser pulses, In the S-1 spectra of the isotopomers, as in the ground state, there are dramatic splittings of what appear to be single bands in the natural isotopic abundance spectrum. The most structurally significant bands of the S-1 state were assigned on the basis of the isotope data, In some cases it was necessary to curve fit unresolved bands in the excited-state spectra in order to account for observed intensity ratios and to rationalize isotope shifts, The changes in band positions on excitation to the S-1 state were compared with those from earlier studies on the T-1 state. The changes in band positions were found to be similar For both excited states. Most notable was the similar shift in nu(2), the most widely used marker band for orbital character. The data are interpreted as implying that the lowest lying singlet state is a configuration interaction admixture of b(1u)b(2g) + a(u)b(3g) configurations with the coefficients weighted heavily in favour of b(1n)b(2g), which Is the configuration of the T-1 state. Copyright (C) 2000 John Wiley & Sons, Ltd.

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. I. General formalism and application to open-shell states

The solution of the time-dependent Schrodinger equation for systems of interacting electrons is generally a prohibitive task, for which approximate methods are necessary. Popular approaches, such as the time-dependent Hartree-Fock (TDHF) approximation and time-dependent density functional theory (TDDFT), are essentially single-configurational schemes. TDHF is by construction incapable of fully accounting for the excited character of the electronic states involved in many physical processes of interest; TDDFT, although exact in principle, is limited by the currently available exchange-correlation functionals. On the other hand, multiconfigurational methods, such as the multiconfigurational time-dependent Hartree-Fock (MCTDHF) approach, provide an accurate description of the excited states and can be systematically improved. However, the computational cost becomes prohibitive as the number of degrees of freedom increases, and thus, at present, the MCTDHF method is only practical for few-electron systems. In this work, we propose an alternative approach which effectively establishes a compromise between efficiency and accuracy, by retaining the smallest possible number of configurations that catches the essential features of the electronic wavefunction. Based on a time-dependent variational principle, we derive the MCTDHF working equation for a multiconfigurational expansion with fixed coefficients and specialise to the case of general open-shell states, which are relevant for many physical processes of interest. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3600397]

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. II. Coulomb interaction effects in single conjugated polymer chains

Conjugated polymers have attracted considerable attention in the last few decades due to their potential for optoelectronic applications. A key step that needs optimisation is charge carrier separation following photoexcitation. To understand better the dynamics of the exciton prior to charge separation, we have performed simulations of the formation and dynamics of localised excitations in single conjugated polymer strands. We use a nonadiabatic molecular dynamics method which allows for the coupled evolution of the nuclear degrees of freedom and of multiconfigurational electronic wavefunctions. We show the relaxation of electron-hole pairs to form excitons and oppositely charged polaron pairs and discuss the modifications to the relaxation process predicted by the inclusion of the Coulomb interaction between the carriers. The issue of charge photogeneration in conjugated polymers in dilute solution is also addressed. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3600404]

Resonance Raman probing of the interaction between dipyridophenazine complexes of Ru(II) and DNA

Resonance Raman (RR) spectroscopy has been used to probe the interaction between dipyridophenazine (dppz) complexes of ruthenium(II), [Ru(L)(2)(dppz)](2+) (L = 1,10-phenanthroline (1) and 2,2-bipyridyl (2)), and calf-thymus DNA. Ground electronic state RR spectra at selected probe wavelengths reveal enhancement patterns which reflect perturbation of the dppz-centered electronic transitions in the UV-vis spectra in the presence of DNA. Comparison of the RR spectra recorded of the short-lived MLCT excited states of both complexes in aqueous solution with those of the longer-lived states of the complexes in the DNA environment reveals changes to excited state modes, suggesting perturbation of electronic transitions of the dppz ligand in the excited state as a result of intercalation. The most prominent feature, at 1526 cm(-1), appears in the spectra of both 1 and 2 and is a convenient marker band for intercalation. For 1, the excited state studies have been extended to the A and A enantiomers. The marker band appears at the same frequency for both but with different relative intensities. This is interpreted as reflecting the distinctive response of the enantiomers to the chiral environment of the DNA binding sites. The results, together with some analogous data for other potentially intercalating complexes, are considered in relation to the more general application of time-resolved RR spectroscopy for investigation of intercalative interactions of photoexcited metal complexes with DNA.

Raman spectroelectrochemical studies and crystal structure of a binuclear copper(I) complex with a bridging diimine ligand

Raman spectroelectrochemical and X-ray crystallographic studies have been made for the binuclear copper(I) complex, [(Ph(3)P)(2)Cu(dpq)Cu(PPh(3))(2)][BF4](2), where dpq is the bridging ligand 2,3-di(2-pyridyl)quinoxaline. The X-ray data show that the pyridine rings are twisted out of plane with respect to the quinoxaline ring which is itself non-planar. The UV/VIS spectra of the metal-to-ligand charge-transfer excited state and those of the electrochemically reduced complex are similar. The resonance-Raman spectrum of the latter species exhibits little change in the frequency of the pyridinylquinoxaline inter-ring C-C bond stretching mode, compared to the ground electronic state. This suggests minimum change in the inter-ring C-C bond order in the electrochemically or charge-transfer generated radical anion. Semiempirical molecular-orbital calculations on both the neutral dpq and radical anion show two near-degenerate lowest unoccupied orbitals in the neutral species. One is strongly bonding across the inter-ring C-C bond while the other is almost nun-bonding. The Raman data suggest that it is this latter orbital which is populated in the transient and electrochemical experiments.

RESONANCE RAMAN-SPECTRA OF THE TRIPLET-STATE OF FREE-BASE TETRAPHENYLPORPHYRIN AND 6 OF ITS ISOTOPOMERS

The resonance Raman spectra of the ground state and the lowest excited tripler state of free-base tetraphenylporphyrin and six of its isotopomers have been obtained using two-color time-resolved techniques. Ground-state spectra were recorded using low-energy 447 nm probe laser pulses, and triplet-state spectra were probed, with similar pulses, 30 ns after high-energy excitation with 532 nm pump pulses. Polarization data on both the ground and triplet states are also reported. The resonance Raman spectrum of the triplet is very different from that of the ground state but the combination of extensive isotope substitution with polarization data allows bands in the ground state to be assigned and corresponding bands in the tripler state to be located. Isotope shifts of the same bands in the S-0 and T-1 states are similar, implying that the compositions of the vibrational modes do not change significantly on excitation. Two of the strongest bands in the T-1 spectra are associated with phenyl ring substituents; these are shifted less than 5 cm(-1) between the S-0 and T-1 states so that bonding in the phenyl substituents is barely affected by excitation to the T-1 state. The changes in position of the porphyrin ring bands are larger, but still only tens of cm(-1) or less, the main changes in the spectra being due to differences in relative band intensities in the two states. The relatively small shifts in the porphyrin ring band positions which are observed show that the excitation energy is not localized on a single small region of the molecule but is delocalized over the entire porphyrin skeleton. This picture of an excited species with high chemical reactivity, but with individual bonds only slightly perturbed from the ground state, is contrasted with molecules, such as benzophenone, where excitation causes a large perturbation in the bonding within a single functional group.

High harmonic generation by halogen anions and noble gas atoms in a laser field

A comparative study of high harmonic generation (HHG) by atoms and ions with active p-electrons is carried out in the theoretical framework of the rescattering mechanism. The substate with m(l) = 0, i.e. zero orbital momentum projection along the electric vector of a linearly polarized laser wave, is found to give the major contribution to the HHG rate. Our calculations for HHG by an H atom in an excited 2p-state demonstrate that the rate for recombination into a final state with a different value of m(l) (= +/- 1), is higher for lower harmonic orders N, while for higher N (beyond the plateau domain) the difference vanishes. For species with closed electron shells, the m(l)-changing transitions are forbidden by the Pauli exclusion principle. We report absolute HHG rates for halogen ions and noble gas atoms at various intensities. These results demonstrate that the Coulomb binding potential of the atoms considerably enhances both the ionization and recombination steps in the rescattering process. However, the weak binding energy of the anions allows lower orders of HHG to be efficiently produced at relatively low intensities, from which we conclude that observation of HHG by an anion is experimentally feasible.

Effect of plasticizer viscosity on the sensitivity of an [RU(bpy)(3)(2+)(Ph4B-)(2)]-based optical oxygen sensor

The quenching of the electronically-excited, lumophoric state of [Ru(bpy)(3)(2+)(Ph4B-)(2)] by oxygen is studied in a wide variety of neat plasticizers. The Stern-Volmer constant, K-SV, is found to be inversely dependent upon the viscosity of the quenching medium, although the natural lifetime of the electronically excited state of [RU(bPY)(3)(2+)(Ph4B-)(2)] is largely independent of medium. The least viscous of the plasticizers tested, triethyl phosphate, did not, however, produce highly sensitive optical oxygen sensors when used to plasticize [RU(bPY)(3)(2+)(Ph4B-)(2)]-containing cellulose acetate butyrate (CAB) and poly(methyl methacrylate) (PMMA) films, Instead, the compatibility of the polymer-plasticizer combination, as measured by the difference in the values of the solubility parameter of the two, appears to be a major factor in determining the overall oxygen sensitivity of the thin plastic films. For highly compatible polymer-plasticizer combinations, the plasticizer with the lowest viscosity produces films of the highest oxygen sensitivity. This situation arises because in the film the quenching process is partly diffusion-controlled and, as a result, the quenching rate constant is inversely proportional to the effective viscosity of the reaction medium.

CROSS-SECTIONS FOR RESONANT TRANSFER AND EXCITATION IN FEQ++H-2 COLLISIONS

Resonant transfer and excitation (RTE) is investigated for Fe(q+) ions (q=23, 24, and 25) colliding with H2. For each charge state, cross sections for RTE were obtained from measurements of K x rays, emitted from the doubly excited intermediate state, coincident with single-electron capture by the incident ion. Additionally, for Fe25+ cross sections were obtained from measurements of coincidences between the two K x rays emitted from the intermediate state. These latter measurements Provide information on the lifetimes of intermediate metastable states formed in the RTE process. In all cases, measured cross sections are in good agreement with calculations based on theoretical cross sections for dielectronic recombination (DR). Since RTE closely approximates DR, the results indicate that dielectronic-recombination cross sections involving K-shell excitation can be accurately predicted for highly charged iron ions. The results for Fe25+ show that metastable states are sufficiently short lived to be observable in the RTE (or DR) process for these hydrogenlike ions.

Solution-based synthesis of cobalt-doped ZnO thin films

Undoped and cobalt-doped (1-4 wt.%) ZnO polycrystalline, thin films have been fabricated on quartz substrates using sequential spin-casting and annealing of simple salt solutions. X-ray diffraction (XRD) reveals a wurzite ZnO crystalline structure with high-resolution transmission electron microscopy showing lattice planes of separation 0.26 nm, characteristic of (002) planes. The Co appears to be tetrahedrally co-ordinated in the lattice on the Zn sites (XRD) and has a charge of + 2 in a high-spin electronic state (X-ray photoelectron spectroscopy). Co-doping does not alter the wurzite structure and there is no evidence of the precipitation of cobalt oxide phases within the limits of detection of Raman and XRD analysis. Lattice defects and chemisorbed oxygen are probed using photoluminescence and Raman spectroscopy - crucially, however, this transparent semiconductor material retains a bandgap in the ultraviolet (3.30-3.48 eV) and high transparency (throughout the visible spectral regime) across the doping range. © 2012 Elsevier B.V.

yambo: An ab initio tool for excited state calculations

yambo is an ab initio code for calculating quasiparticle energies and optical properties of electronic systems within the framework of many-body perturbation theory and time-dependent density functional theory. Quasiparticle energies are calculated within the GW approximation for the self-energy. Optical properties are evaluated either by solving the Bethe-Salpeter equation or by using the adiabatic local density approximation. yambo is a plane-wave code that, although particularly suited for calculations of periodic bulk systems, has been applied to a large variety of physical systems. yambo relies on efficient numerical techniques devised to treat systems with reduced dimensionality, or with a large number of degrees of freedom. The code has a user-friendly command-line based interface, flexible 110 procedures and is interfaced to several publicly available density functional ground-state codes.

Time dependence of rotational state populations of excited hydrogen molecules in an RF excited plasma reactor

We report on time-dependent population distributions of excited rotational states of hydrogen in a capacitively coupled RF discharge. The common model to obtain the gas temperature from the rotational distribution is not applicable at all times during the discharge cycle due to the time dependence of the EEDF. The apparent temperature within a cycle assumes values between 350 K and 450 K for the discharge parameters of this experiment. We discuss the optimum time window within the discharge cycle that yields the best approximation to the actual temperature. Erroneous results can be obtained, in principle, with time-integrated measurements; we find, however, that in the present case the systematic error amounts to only approximately 20 K. This is due to the fact that the dominant contribution to the average intensity arises during that time window for which the assumptions underlying the analysis are best fulfilled. A similar analysis can be performed for N+2 rotational bands with a small amount of nitrogen added to the discharge gas. These populations do not exhibit the time variations found in the case of H2.