Origin of electronic absorption spectra of MLCT-excited and one-electron reduced 2,2′-bipyridine and 1,10-phenanthroline complexes

UV–Vis absorption spectra of one-electron reduction products and 3MLCT excited states of [ReICl(CO)3- (N,N)] (N,N = 2,20-bipyridine, bpy; 1,10-phenanthroline, phen) have been measured by low-temperature spectroelectrochemistry and UV–Vis transient absorption spectroscopy, respectively, and assigned by open-shell TD-DFT calculations. The characters of the electronic transitions are visualized and analyzed using electron density redistribution maps. It follows that reduced and excited states can be approximately formulated as [ReICl(CO)3(N,Nÿ)]ÿ and ⁄[ReIICl(CO)3(N,Nÿ)], respectively. UV–Vis spectra of the reduced complexes are dominated by IL transitions, plus weaker MLCT contributions. Excited-state spectra show an intense band in the UV region of 50% IL origin mixed with LMCT (bpy, 373 nm) or MLCT (phen, 307 nm) excitations. Because of the significant IL contribution, this spectral feature is akin to the principal IL band of the anions. In contrast, the excited-state visible spectral pattern arises from predominantly LMCT transitions, any resemblance with the reduced-state visible spectra being coincidental. The Re complexes studied herein are representatives of a broad class of metal a-diimines, for which similar spectroscopic behavior can be expected.

Investigation of Ground- and Excited-State Photophysical Properties of 5,10,15,20-Tetra(4-pyridyl)-21H,23H-porphyrin with Ruthenium Outlying Complexes

The present work employs a set of complementary techniques to investigate the influence of outlying Ru(II) groups on the ground- and excited-state photophysical properties of free-base tetrapyridyl porphyrin (H(2)TPyP). Single pulse and, pulse train Z-scan techniques used M association with laser flash photolysis, absorbance and fluorescence spectroscopy, and fluorescence decay measurements, allowed us to conclude that the presence of outlying Ru(II) groups causes significant changes on both electronic structure and vibrational properties of porphyrin. Such modifications take place mainly due to the activation of. nonradiative decay channels responsible for the emission, quenching, as well as by favoring some vibrational modes in the light absorption process, It is also observed that, differently from what happens when the Ru(II) is placed at the center of the macrocycle, the peripheral groups cause an increase of the intersystem crossing processes, probably due to the structural distortion of the ring that implies a worse spin orbit coupling, responsible for the intersystem crossing mechanism.

Excited state properties of formamide in water solution: An ab initio study

We present ab initio quantum calculation of the optical properties of formamide in vapor phase and in water solution. We employ time dependent density functional theory for the isolated molecule and many-body perturbation theory methods for the system in solution. An average over several molecular dynamics snapshots is performed to take into account the disorder of the liquid. We find that the excited stateproperties of the gas-phase formamide are strongly modified by the presence of the water solvent: the geometry of the molecule is distorted and the electronic and optical properties are severely modified. The important interaction among the formamide and the water molecules forces us to use fully quantum methods for the calculation of the excited stateproperties of this system. The excitonic wave function is localized both on the solute and on part of the solvent.

Excited-State Structure, Vibrations, and Nonradiative Relaxation of Jet-Cooled 5-Fluorocytosine

The S0 → S1 vibronic spectrum and S1 state nonradiative relaxation of jet-cooled keto-amino 5-fluorocytosine (5FCyt) are investigated by two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm–1 resolution. The 000 rotational band contour is polarized in-plane, implying that the electronic transition is 1ππ*. The electronic transition dipole moment orientation and the changes of rotational constants agree closely with the SCS-CC2 calculated values for the 1ππ* (S1) transition of 5FCyt. The spectral region from 0 to 300 cm–1 is dominated by overtone and combination bands of the out-of-plane ν1′ (boat), ν2′ (butterfly), and ν3′ (HN–C6H twist) vibrations, implying that the pyrimidinone frame is distorted out-of-plane by the 1ππ* excitation, in agreement with SCS-CC2 calculations. The number of vibronic bands rises strongly around +350 cm–1; this is attributed to the 1ππ* state barrier to planarity that corresponds to the central maximum of the double-minimum out-of-plane vibrational potentials along the ν1′, ν2′, and ν3′ coordinates, which gives rise to a high density of vibronic excitations. At +1200 cm–1, rapid nonradiative relaxation (knr ≥ 1012 s–1) sets in, which we interpret as the height of the 1ππ* state barrier in front of the lowest S1/S0 conical intersection. This barrier in 5FCyt is 3 times higher than that in cytosine. The lifetimes of the ν′ = 0, 2ν1′, 2ν2′, 2ν1′ + 2ν2′, 4ν2′, and 2ν1′ + 4ν2′ levels are determined from Lorentzian widths fitted to the rotational band contours and are τ ≥ 75 ps for ν′ = 0, decreasing to τ ≥ 55 ps at the 2ν1′ + 4ν2′ level at +234 cm–1. These gas-phase lifetimes are twice those of S1 state cytosine and 10–100 times those of the other canonical nucleobases in the gas phase. On the other hand, the 5FCyt gas-phase lifetime is close to the 73 ps lifetime in room-temperature solvents. This lack of dependence on temperature and on the surrounding medium implies that the 5FCyt nonradiative relaxation from its S1 (1ππ*) state is essentially controlled by the same ∼1200 cm–1 barrier and conical intersection both in the gas phase and in solution.

Ground and Electronic Excited States from Pairing Matrix Fluctuation and Particle-Particle Random Phase Approximation

The accurate description of ground and electronic excited states is an important and challenging topic in quantum chemistry. The pairing matrix fluctuation, as a counterpart of the density fluctuation, is applied to this topic. From the pairing matrix fluctuation, the exact electron correlation energy as well as two electron addition/removal energies can be extracted. Therefore, both ground state and excited states energies can be obtained and they are in principle exact with a complete knowledge of the pairing matrix fluctuation. In practice, considering the exact pairing matrix fluctuation is unknown, we adopt its simple approximation --- the particle-particle random phase approximation (pp-RPA) --- for ground and excited states calculations. The algorithms for accelerating the pp-RPA calculation, including spin separation, spin adaptation, as well as an iterative Davidson method, are developed. For ground states correlation descriptions, the results obtained from pp-RPA are usually comparable to and can be more accurate than those from traditional particle-hole random phase approximation (ph-RPA). For excited states, the pp-RPA is able to describe double, Rydberg, and charge transfer excitations, which are challenging for conventional time-dependent density functional theory (TDDFT). Although the pp-RPA intrinsically cannot describe those excitations excited from the orbitals below the highest occupied molecular orbital (HOMO), its performances on those single excitations that can be captured are comparable to TDDFT. The pp-RPA for excitation calculation is further applied to challenging diradical problems and is used to unveil the nature of the ground and electronic excited states of higher acenes. The pp-RPA and the corresponding Tamm-Dancoff approximation (pp-TDA) are also applied to conical intersections, an important concept in nonadiabatic dynamics. Their good description of the double-cone feature of conical intersections is in sharp contrast to the failure of TDDFT. All in all, the pairing matrix fluctuation opens up new channel of thinking for quantum chemistry, and the pp-RPA is a promising method in describing ground and electronic excited states.

Homo- and heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins : preparation, X-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using pulse transit delay in Z-scan to discriminate between excited-state absorption and other nonlinear processes in ZnO nanocones

We report a new approach that uses the single beam Z-scan technique, to discriminate between excited state absorption (ESA) and two and three photon nonlinear absorption. By measuring the apparent delay or advance of the pulse in reaching the detector, the nonlinear absorption can be unambiguously identified as either instantaneous or transient. The simple method does not require a large range of input fluences or sophisticated pulse-probe experimental apparatus. The technique is easily extended to any absorption process dependent on pulse width and to nonlinear refraction measurements. We demonstrate in particular, that the large nonlinear absorption in ZnO nanocones when exposed to nanosecond 532 nm pulses, is due mostly to ESA, not pure two-photon absorption.

Multiband photoluminescence from carbon nanoflakes synthesized by hot filament CVD: towards solid-state white light sources

Carbon nanoflakes (CNFLs) are synthesized on silicon substrates deposited with carbon islands in a methane environment using hot filament chemical vapor deposition. The structure and composition of the CNFLs are studied using field emission scanning electron microscopy, high-resolution transmission electron microscopy, micro-Raman spectroscopy, and X-ray photoelectron spectroscopy. The results indicate that the CNFLs are composed of multilayer graphitic sheets and the area and thickness of CNFs increase with the growth time. The photoluminescence (PL) of CNFLs excited by a 325 nm He-Cd laser exhibits three strong bands centered at 408, 526, and 699 nm, which are related to the chemical radicals terminated on the CNFLs and the associated interband transitions. The PL results indicate that the CNFLs are promising as an advanced nano-carbon material capable of generating white light emission. These outcomes are significant to control the electronic structure of CNFLs and contribute to the development of next-generation solid-state white light emission devices. © 2014 the Partner Organisations.

Excited-state dynamics in diketopyrrolopyrrole-based copolymer for organic photovoltaics investigated by transient optical spectroscopy

We investigate the photoexcited state dynamics in a donor-acceptor copolymer, poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]- pyrrole-1,4-dione-alt-naphthalene} (pDPP-TNT), by picosecond fluorescence and femtosecond transient absorption spectroscopies. Timeresolved fluorescence lifetime measurements of pDPP-TNT thin films reveal that the lifetime of the singlet excited state is 185 ± 5 ps and that singlet-singlet annihilation occurs at excitation photon densities above 6 × 1017 photons/cm3. From the results of singlet-singlet annihilation analysis, we estimate that the single-singlet annihilation rate constant is (6.0 ± 0.2) × 109cm3 s-1 and the singlet diffusion length is -7 nm. From the comparison of femtosecond transient absorption measurements and picosecond fluorescence measurements, it is found that the time profile of the photobleaching signal in the charge-transfer (CT) absorption band coincides with that of the fluorescence intensity and there is no indication of long-lived species, which clearly suggests that charged species, such as polaron pairs and triplet excitons, are not effectively photogenerated in the neat pDPP-TNT polymer.

Properties of the correlated electronic states of pyrene and hydrogenated pyrene

Approximate calculations are reported on pyrene within the PPP model Hamiltonian using a novel restricted CI scheme which employs both molecular orbital and valence bond techniques. Also reported are detailed full CI results of the PPP model on 2,7-dihydropyrene obtained using the valence bond method. Spectral studies, charge and spin density calculations in ground and excited states, and ring current calculations in the ground state of the molecules are presented. In pyrene, the calculated excitation energies are in good agreement with experiment. The closed structure pi-conjugated molecule pyrene appears to show smaller distortions from the ground state geometry compared with the open structure pi-conjugated molecule 2,7-dihydropyrene. The ground state equilibrium structure of 2,7-dihydropyrene can be viewed as two hexatriene molecules connected by a vinyl crosslink, as is evident from bond order and ring current calculations. This is consistent with the only Kekule resonant structure possible for this molecule.

Electronic Properties of the Vortex State in Cuprate Superconductors

The superconducting state of the cuprates in the presence of a magnetic field has been investigated very actively in the past few years through measurements of electrical and thermal transport, ac conductivity, specific heat, and other quantities. The observed behavior is not well understood; it probes the nature of quasiparticies, vortices, and their interactions in a superconductor with nodes in the pair amplitude. We summarize here experimental results and our attempts to understand the phenomena.

Binding of three molecules in the excited state

t is shown that three neutral molecules can form a stable trimer if one of them is in the excited state. The formation of termolecular electron donor-acceptor complexes of sequence DDA and DAA arises from charge-resonance interaction.

The Mechanism Of The Hydrogen Abstraction Process By Photo-Excited Ketones

Qualitative potential energy surfaces for hydrogen abstraction from alkanes containing primary, secondary and tertiary C-H bonds by a photo-excited ketone have been reported, The results suggest that the activation barriers for these processes decrease in the order primary > secondary > tertiary in agreement with the observed trend in the rate constants. The analysis of the electronic structure of the transition-state reveal that electron-transfer from hydrocarbon to ketone and formation of a new bond are almost synchronous in the hydrogen transfer process. The tunneling of hydrogen is not important in the normal temperature region even though the barriers are small.