Resonance de-enhancement in the 2(1)A(g) state of trans-azobenzene

We analyze the origin of de-enhancement for a number of vibrational modes in the 2(1)A(g) excited state of trans-azobenzene. We have used the time-dependent wave packet analysis of the RR intensities by including the multimode damping effects in the calculation. This avoids the use of unrealistically large values for the damping parameter. It is concluded that the de-enhancement is caused by the interference between the two uncoupled electronic states, and that the intensities observed under the so-called symmetry forbidden 2(1)A(g) <-- 1(1)A(g) transition are purely due to resonance excitation. It is also observed that the use of the time-dependent approach to study the de-enhancement effects caused by multiple electronic states on the RR intensities is not necessarily useful if one is interested in the structural dynamics.

Investigation of short-time isomerization dynamics in p-nitroazobenzene from resonance Raman intensity analysis

Resonance Raman (RR) spectra are presented for p-nitroazobenzene dissolved in chloroform using 18 excitation Wavelengths, covering the region of (1)(n --> pi*) electronic transition. Raman intensities are observed for various totally symmetric fundamentals, namely, C-C, C-N, N=N, and N-O stretching vibrations, indicating that upon photoexcitation the excited-state evolution occurs along all of these vibrational coordinates. For a few fundamentals, interestingly, in p-nitroazobenzene, it is observed that the RR intensities decrease near the maxima of the resonant electronic (1)(n --> pi*) transition. This is attributed to the interference from preresonant scattering due to the strongly allowed (1)(pi --> pi*) electronic transition. The electronic absorption spectrum and the absolute Raman cross section for the nine Franck-Condon active fundamentals of p-nitroazobenzene have been successfully modeled using Heller's time-dependent formalism for Raman scattering. This employs harmonic description of the lowest energy (1)(n --> pi*) potential energy surface. The short-time isomerization dynamics is then examined from a priori knowledge of the ground-state normal mode descriptions of p-nitroazobenzene to convert the wave packet motion in dimensionless normal coordinates to internal coordinates. It is observed that within 20 fs after photoexcitation in p-nitroazobenzene, the N=N and C-N stretching vibrations undergo significant changes and the unsubstituted phenyl ring and the nitro stretching vibrations are also distorted considerably.

Metastable morphotropic phase boundary state in the multiferroic BiFeO3-PbTiO3

Temperature-time study of the magnetoelectric multiferroic (1-x)BiFeO3-(x)PbTiO3 by x-ray and electron diffraction on the reported morphotropic phase boundary (MPB) compositions revealed that this MPB does not correspond to the equilibrium state. The MPB like state is rather of metastable nature and arise due to kinetic arrest of metastable rhombohedral (R3c) phase, along with the equilibrium tetragonal (P4mm) phase. The life time of the metastable R3c nuclei is very sensitive to composition and temperature, and nearly diverges at x -> 0.27. The MPB like state appears only if the system is cooled before the metastable R3c nuclei could vanish. These findings resolve the long standing controversy with regard to seemingly erratic phase formation behaviour reported by different groups and provides a rational basis for developing genuine equilibrium MPB compositions in this system for better piezoelectric properties. (C) 2013 AIP Publishing LLC.

Kinetically stabilized C-60-toluene solvate nanostructures with a discrete absorption edge enabling supramolecular topotactic molecular exchange

Nanosized fullerene solvates have attracted widespread research attention due to recent interesting discoveries. A particular type of solvate is limited to a fixed number of solvents and designing new solvates within the same family is a fundamental challenge. Here we demonstrate that the hexagonal closed packed (HCP) phase of C-60 solvates, formed with m-xylene, can also be stabilized using toluene. Contrary to the notion on their instability, these can be stabilized from minutes up to months by tuning the occupancy of solvent molecules. Due to high stability, we could record their absorption edge, and measure excitonic life-time, which has not been reported for any C-60 solvate. Despite being solid, absorbance spectrum of the solvates is similar in appearance to that of C-60 in solution. A new absorption band appears at 673 nm. The fluorescence lifetime at 760 nm is similar to 1.2 ns, suggesting an excited state unaffected by solvent-C-60 interaction. Finally, we utilized the unstable set of HCP solvates to exchange with a second solvent by a topotactic exchange mechanism, which rendered near permanent stability to the otherwise few minutes stable solvates. This is also the first example of topotactic exchange in supramolecular crystal, which is widely known in ionic solids. (C) 2014 Elsevier Ltd. All rights reserved.

Excited electronic state decomposition mechanisms of clusters of dimethylnitramine and aluminum

In this report, electronically non-adiabatic decomposition pathways of clusters of dimethylnitramine and aluminum (DMNA-Al and DMNA-Al-2) are discussed in comparison to isolated dimethylnitramine (DMNA). Electronically excited state processes of DMNA-Al and DMNA-Al-2 are explored using the complete active space self-consistent field (CASSCF) and the restricted active space self-consistent field (RASSCF) theories, respectively. Similar to the nitro-nitrite isomerization reaction pathway of DMNA, DMNA-Al-n clusters also exhibit isomerization pathway. However, it involves several other steps, such as, first Al-O bond dissociation, then N-N bond dissociation followed by isomerization and finally NO elimination. Furthermore, DMNA-Al-n clusters exhibit overall exothermic decomposition reaction pathway and isolated DMNA shows overall endothermic reaction channel.

Time-dependent density-functional calculations for optical spectra of Na-2 and Na-4 clusters

With the frame of the time-dependent local density approximation, an efficient description of the optical response of clusters has been used to study the photo-absorption cross section of Na-2 and Na-4 clusters. It is shown that our calculated results are in good agreement with the experiment. In addition, our calculated spectrum for the Na-4 cluster is in better agreement with experiment than the GW absorption spectrum.

Dynamics of excited m-dichlorobenzene

Dynamics of excited m-dichlorobenzene is investigated in real time by femtosecond pump-probe method, combined with time-of-flight mass spectrometric detection in a supersonic molecular beam. The yields of the parent ion and daughter ion C6H4CI+ are examined as a function of the delay between the 270 and 810 nm femtosecond laser pulses, respectively. The lifetime of the first singlet excited state S-1 of m-dichlorobenzene is measured. The origin of this daughter ion C6H4CI+ is discussed. The ladder mechanism is proposed to form the fragment ion. In addition, our experimental results exhibit a rapid damped sinusoidal oscillation over intermediate time delays, which is due to quantum beat effects.

Dynamics of excited OCS investigated by resonance-enhanced multiphoton ionization

The predissociation decay behavior of molecule carbonyl sulfide (OCS) has been investigated by resonance-enhanced multiphoton ionization spectroscopy using the pump-probe technique of dichroic femtosecond lasers in real time. The lifetime of excited OCS around 74 720 cm(-1) by two-photon absorption of 268 nm, corresponding to upsilon(1)=1 of the Rydberg state [(2)Pi(1/2)]4ppi((1)Sigma(+)), is directly determined to be tau(D)=1071+/-11 fs. This picosecond decay process indicates that the excited state is predissociative. The temporal information of dissociation enriches the knowledge of the potential-energy surface of the associative excited state.

Substitution effect of nitrogen atoms with carbon atoms in porphyrin on the electronic structure and excited states properties

Density functional theory (DFT) electronic structure calculations were carried out to predict the structures and the absorption and emission spectra for porphyrin and a series of carbaporphyrins-carbaporphyrin, adj-dicarbaporphyrin, opp-dicarbaporphyrin, tricarbaporphyrin and tetracarbaporphyrin. The ground- and excited-state geometries were optimized at the B3LYP/6-31g(d) and CIS/6-31g(d) level, respectively. The optimized ground-state geometry and absorption spectra of porphyrin, calculated by DFT and time-dependent DFT (TDDFT), are comparable with the available experimental values. Based on the optimized excited-state geometries obtained by CIS/6-31g(d) method, the emission properties are calculated using TDDFT method at the B3LYP/6-31g(d) level. The effects of the substitution of nitrogen atoms with carbon atoms at the center positions of porphyrin are discussed. The results indicate that the two-pyrrole nitrogens are important to the chemical and physical properties for porphyrin.

Calculations of cross sections of resonant two-photon transitions to the second excited 4f5d state in Pr3+: Y3Al5O12 using density matrix theory

The density matrix resonant two-photon absorption (TPA) theory applicable to laser crystals doped with rare earth ions is described. Using this theory, resonant TPA cross sections for transitions from the ground state to the second excited state of the 4f5d configuration in cm(4)s Pr3+:Y3Al5O12 are calculated. The peak value of TPA cross section calculated is 2.75 x 10(-50) cm(4)s which is very close to the previous experimental value 4 x 10(-50) cm(4) s. The good agreement of calculated data with measured values demonstrates that the density matrix resonant TPA theory can predict resonant TPA intensity much better than the standard second-order perturbation TPA theory.

Spectroscopic measurements of phase-resolved electron energy distribution functions in RF-excited discharges

The reliable measurement of the electron energy distribution function (EEDF) of plasmas is one of the most important subjects of plasma diagnostics, because this piece of information is the key to understand basic discharge mechanisms. Specific problems arise in the case of RF-excited plasmas, since the properties of electrons are subject to changes on a nanosecond time scale and show pronounced spatial anisotropy. We report on a novel spectroscopic method for phase- and space-resolved measurements of the electron energy distribution function of energetic (> 12 eV) electrons in RF discharges. These electrons dominate excitation and ionization processes and are therefore of particular interest. The technique is based on time-dependent measurements during the RF cycle of excited-state populations of rare gases admixed in small fractions. These measurements yield � in combination with an analytical model � detailed information on the excitation processes. Phase-resolved optical emission spectroscopy allows us to overcome the difficulties connected with the very low densities (107�109 cm�3) and the transient character of the electrons in the sheath region. The EEDF of electrons accelerated in the sheath region can be described by a shifted Maxwellian with a drift velocity component in direction of the electric field. The method yields the high-energy tail of the EEDF on an absolute scale. The applicability of the method is demonstrated at a capacitively coupled RF discharge in hydrogen.

TIME-RESOLVED RESONANCE RAMAN-SPECTROSCOPY AND RAMAN SPECTROELECTROCHEMISTRY OF (CO)(5)W[4,4'-BPY]W(CO)(5), PROBED IN THE VISIBLE AND NEAR-INFRARED

Time-resolved resonance Raman spectroscopy of the lowest energy excited state of the 4,4'-bipyridyl ligand-bridged complex, [(CO)(5)W(L)W(CO5] (1), and Raman spectroscopy of electrochemically reduced 1, both give bands characteristic of the the L(.-) species. This confirms that the ligand L is negatively charged in the lowest energy exicited state which is therefore metal-ligand charge transfer (MLCT) in character. Raman spectra of the radical anion of 1 excited in the far red (800 nm) exhibited a band near 2050 cm(-1) due to a vco symmetric CO stretching mode, compared to the corresponding band at 2070 cm(-1) in the spectrum of the parent, uncharged complex. The lower vco in the reduced complex supports the recent finding by time-resolved IR spectroscopy of a similar frequency decrease for nu(CO) in the longest lived (MLCT) excited state of 1 which was attributed to electron/hole localisation in this state on the IR time scale.

CONTRIBUTION OF RESONANCE RAMAN EXCITATION SPECTROSCOPY FOR PROBING ELECTRONICALLY EXCITED-STATES - NATURE OF A PORPHYRIN-DNA EXCIPLEX

The resonance Raman spectra of a water-soluble metalloporphyrin Cu(TMpy-P4), complexed with a synthetic nucleic acid, poly(dA-dT), were measured by using excitation wavelengths located within the B (Soret) transition of the porphyrin (417-470 nm), while its excited state was synchronously pumped with 545-nm pulsed excitation corresponding to the Q transition. In the presence of pump pulses, the aqueous solution of the Cu(TMpy-P4).poly(dA-dT) complex exhibits resonance Raman bands at 1558 and 1353 cm-1 that are not observed in the absence of pump pulses. These new features were previously assigned to electronically excited Cu(TMpy-P4), stabilized by forming an exciplex with the A-T sites of the nucleic acid. Here we present resonance Raman excitation profiles (RREP) of both the excited and ground states of the complex, and we experimentally confirm the very short lifetime of the exciplex. To our knowledge this is the first time that a RREP of a very short lived (ca. 20 ps) intermediate excited state has been obtained with a two-color experiment. We use this to help to characterize the nature of the porphyrin-AT specific complex formed in the porphyrin excited state.

Time-resolved studies of neutral and ionized Na_n clusters with femtosecond light pulses

The real-time dynamics of Na_n (n=3-21) cluster multiphoton ionization and fragmentation has been studied in beam experiments applying femtosecond pump-probe techniques in combination with ion and electron spectroscopy. Three dimensional wave packet motions in the trimer Na_3 ground state X and excited state B have been observed. We report the first study of cluster properties (energy, bandwidth and lifetime of intermediate resonances Na_n^*) with femtosecond laser pulses. The observation of four absorption resonances for the cluster Na_8 with different energy widths and different decay patterns is more difficult to interpret by surface plasmon like resonances than by molecular structure and dynamics. Timeresolved fragmentation of cluster ions Na_n^+ indicates that direct photo-induced fragmentation processes are more important at short times than the statistical unimolecular decay.