Metastable optical absorption of exited F-centers in BeO crystals

The metastable optical absorption in additively colored BeO crystals is studied. It is found that the optical absorption is induced by transitions between the excited triplet and singlet states of an F-center.     

Defect formation and VUV luminescence in BaF 2

Nominally pure BaF 2 single crystals were investigated at 77 v K with optical absorption and electron paramagnetic resonance to understand the mechanism of radiation damage. We find that X-irradiation at 77 v K of undoped BaF 2 produces V k - and F -centres having absorption bands at 3.4 and 2.3 v eV respectively.     

Investigations on the Photoreactions of Phenothiazine and Phenoxazine in Presence of 9-cyanoanthracene by Using Steady State and Time Resolved Spectroscopic Techniques

By using electrochemical, steady state and time resolved (fluorescence lifetime and transient absorption) spectroscopic techniques, detailed investigations were made to reveal the mechanisms of charge separation or forward electron transfer reactions within the electron donor phenothiazine (PTZH) or phenoxazine (PXZH) and well known electron acceptor 9-cyanoanthracene (CNA). The transient absorption spectra suggest that the charge separated species formed in the excited singlet state resulted from intermolecular photoinduced electron transfer reactions within the donor PTZH (or PXZH) and CNA acceptor relaxes to the corresponding triplet state. Though alternative mechanisms of via formations of contact neutral radical by H-transfer reaction have been proposed but the observed results obtained from the time resolved measurements indicate that the regeneration of ground state reactants is primarily responsible due to direct recombination of triplet contact ion-pair (CIP) or solvent-separated ion-pair (SSIP).     

Creation and optical properties of stable and metastable hole-trapped centres in beryllium oxide

Abstract

The paper is devoted to study of formation mechanisms and optical absorption of the hole-trapped centers in neutron, electron-impulse and X-irradiated BeO crystals. V⁰ and V^? centers are found out to be formed as a result of neutron irradiation creating cation Frenkel pairs. Within the transient absorption decay kinetics, we registered a component whose thermal-time properties coincide with those of the luminescence of triplet self-trapped excitons. A number of absorption bands from the V_B center and exciton hole nucleus are interpreted as transitions between the O^? ion p-levels splitted by the crystal field, as well as polaron transitions and transitions into the valence band.     

Intersystem crossing in oligothiophenes studied by fs time-resolved spectroscopy

High triplet quantum yields of more than 90% for bithiophene and terthiophene have to be connected with very fast and effective formation of triplets after excitation. We studied these processes with fs pump–probe spectroscopy. The time behaviour of transient optical spectra within the singlet and triplet manifold was examined for bi- and terthiophene (2T and 3T) in solution. For 2T we used two-photon absorption for excitation. We found transient spectra of the excited singlet state, the triplet state and that of radical cations. The kinetics of the excited-state absorption was described by a bi-exponential function. Additionally we observed formation and recombination of radical cations. The recombination is connected with triplet formation. Both processes could be described by a time constant of 62 ps±9 ps. For 3T we found a dependence of the processes on excitation energy using one-photon absorption. The triplet quantum yield increased with higher excitation energy. The kinetics becomes bi-exponential with increasing amplitude of the short time constant of 2 ps at increasing excitation energy. The main reasons for the effective intersystem crossing (ISC) in both oligothiophenes are – besides the high spin-orbit coupling factor introduced by the sulphur atom – the almost isoenergetic positions of the S ₁ and T ₂ states, detected by PD-PES [1]. At higher photon excitation energy for 3T above the band gap an additional channel for ISC was detected. We believe that during the geometric change from the non-relaxed non-planar to the relaxed planar excited state S ₁, ultrafast intersystem crossing takes place. Received: 6 December 1999 / Published online: 2 August 2000     

Effect of halogen atom on electron spin polarization studied by CIDEP,using halogen substituted aromatic acyl compounds

The reaction and spin dynamics of the photocleavage reaction of 2-chloro-2′-acetylnaphthalene were studied by time-resolved FT-EPR and transient absorption (TA) spectroscopy. The photocleavage reaction from both singlet and triplet states was observed by TA and EPR experiments, although the radical cleavage reaction in the excited triplet state is energetically unfavourable. This feature has been explained by the ionic cleavage reaction due to the electro-negativity of the chlorine atoms. The time-resolved FT-EPR spectra were similar to those observed in the bromine substituted compound, 2-BAN, reported in a previous paper. The origin of the electron spin polarization was assigned to the radical triplet pair mechanism (RTPM) and free radical pair mechanism (F-pair RPM) from analysis of the time profiles of the spin polarization.     

Photoinduced light absorption by C60 films in the 0.08–4.0-eV spectral range

Spectra of photoinduced light absorption in C₆₀ films at high and low excitations in the temperature range between 15 and 300 K have been measured. In addition to the well-known explanation of photoinduced absorption in terms of optical transitions in the system of photogenerated singlet excitons, triplet excitons, and polarons, changes in the absorption spectrum of the fullerite ground state must be considered. We suggest taking into account the effect of crystal field in explaining the features of the photoinduced absorption spectrum. A feature similar to the inverted luminescence spectrum and ascribed to optical excitation of singlet excitons, which is partially allowed owing to intermolecular interaction, has been detected in spectrum of photoinduced absorption. Zh. éksp. Teor. Fiz. 112, 246–256 (July 1997)     

四苯基卟啉—锌化合物的微微秒瞬态吸收和荧光动力学研究

用微微秒瞬态吸收和荧光动力学测量方法,研究了四苯基卟啉-锌的三重态建立过程和单重态的衰减过德;测量了样品的系际交叉速率、单重态的寿命及其对532nm波长的吸收截面.     

Photocleavage reaction of bromine substituted aromatic acyl compounds studied by CIDEP and transient absorption spectroscopy

The photocleavage of the CBr bond in bromoacetylnaphthalene is investigated by transient absorption and time resolved EPR spectroscopy. In the transient absorption of 2-bromo-2′-acetylnaphthalene, the absorption band observed at λ_max ~440 nm is assigned to the triplet state of the parent molecule. After decay of the triplet absorption, a long lived absorption band is observed at λ_max ~380 nm, which is assigned to naphthoylmethyl radical. The yield of this radical is not dependent on the concentration of oxygen even though the absorption band of the triplet state was quenched by addition of oxygen. Thus we conclude that the spin multiplicity of the precursor molecule is singlet. The CW time resolved EPR spectrum shows a typical E?/A CIDEP pattern of three hyperfine lines of the naphthoylmethyl radical. This result suggests some contribution from triplet precursor molecules. However, a careful analysis of the time profile of the CIDEP intensity observed by FT-EPR revealed that the polarization is generated from the radical pair mechanism (RPM) from the encountered pair of two free naphthoylmethyl radicals and the radical-triplet pair mechanism. RPM polarization by the geminate radical pair, formed by the Br atom and the naphthoylmethyl radical, is not observed. This fact indicates that large spin-orbit coupling (Δg and/or fast spin relaxation by g anisotropy) spoils the RPM polarization. The finding is in contrast to the recent observation of RPM polarization in the Cl cleavage reaction of 1-(chloromethyl)naphthalene.     

Statics and dynamics of excited states of oxygen-deficient centers in SiO<Subscript>2</Subscript>

The parameters of excited states of oxygen-deficient centers (ODCs) in high-energy-electron irradiated crystalline and glassy SiO₂ have been studied using optical absorption, luminescence, and photoelectron emission spectroscopy. Additional evidence has been gained in support of the model of a neutral oxygen vacancy in ODCs, the diagram of electronic transitions has been refined, and their characteristics have been quantified. The possibility of ionization of the singlet and triplet defect states at a transition to the anomalously relaxed configuration has been demonstrated using the particular example of α-ODCs. Nonradiative excitation transfer from nonbridging oxygen centers to the triplet ODC state has been observed.     

Fluorescence studies of retinol and retinyl acetate

The polarized emission study of all-trans retinol and retinyl acetate in solid films at room temperature has been carried out. The shape of the absorption and fluorescence is typical of Franck-Condon forbidden bands. The high positive polarization of the fluorescence excitation and the emission (when excited into main absorption band due to 1_Bu ← 1_Ag transition) suggests that the lowest excited singlet state of retinols has a large amount of 1_Bu character. The explanation for the high positive polarization involving strong vibronic interactions suggesting 1_Ag - (a very weakly allowed state) being the lowest excited singlet has also been considered.     

B-type delayed fluorescence of rubreneperoxide in solution.

B-type of delayed fluorescence was observed for the first time for rubreneperoxide. Rubreneperoxide molecules were excited in a two step process. In the first step an excited singlet S₁ is created, which undergoes intersystem crossing to T₁; then T-T absorption creates an excited triplet rubreneperoxide molecule, which returns to the first excited singlet level by intersystem crossing. The recreated first excited singlet of rubreneperoxide decays back to the ground state by emitting B-type of delayed fluorescence.     

Excited singlet and triplet states of aromatic hydrocarbons determined by a laser photolysis technique

A kinetic spectrophotometric technique, employing a Q-switched, frequency-doubled ruby laser as the excitation source, has been used to determine the short-lived (S₁ → S_p), and long-lived (T₁ → T_q) transient absorption spectra of several benzenoid aromatic hydrocarbons. The excited singlet states determined in this way are compared with the singlet states observed by absorption from the ground state (S₀ → S_n). Some previously assigned triplet states are reassigned as singlet levels.     

High Resolution B-Type Delayed Fluorescence of Dibenzanthracene in PMMA

B-Type delayed fluorescence of 1,2,3,4-dibenzanthracene in PMMA was experimentally observed for the first time. Dibenzanthracene molecules were exerted in a two-step process. In the first step, an excited singlet S₁ is created, which undergoes intersystem crossing to T₁ then T-T absorption creates an excited triplet dibenzanthracene molecule, which returns to the first exerted singlet level by intersystem crossing. The recreated first excited singlet of dibenzanthracene decays back to the ground state by emitting this new type of delayed fluorescence.     

Excited state absorption of Ag--centres in RbBr

The induced absorption of Ag^--centres in RbBr pumped by a strong excimer laser pulse is measured over a wide spectral range (250 to 950 nm) using a weak cw probe beam (Xe-lamp). A strong transient absorption around 510 nm is observed and is attributed to the intraionic transition from the relaxed excited 5 ³P₁ state to upper S- or D-levels.     

Photophysical studies on axially substituted indium and gallium phthalocyanines upon UV-Vis laser irradiation

A series of results from different photophysical experiments on indium and gallium phthalocyanine (Pc) compounds is reported. Gallium Pc's have much longer singlet and triplet excited state lifetimes in comparison with indium Pc's. The strong reverse saturable absorption observed at 532 nm excitation is a consequence of the increase in absorbance of Pc's in the triplet excited state in the optical window comprised between Q- and B-bands, as verified upon laser irradiation with ns pulses at 355 nm. Using C₆₀ as a reference, the intersystem cross quantum yields of tBu₄PcInCl and tBu₄PcGaCl are 0.70 and 0.36, respectively.     

Transient absorption spectroscopy of a monofullerene C<Subscript>60</Subscript>-bis-(pyropheophorbide <Emphasis Type="Italic">a</Emphasis>) molecular system in polar and nonpolar environments

The population dynamics of the excited and ground states of the monofullerene-bis (pyropheophorbide a) complex (FP1) were studied in polar (DMF) and nonpolar (toluene) solvents using picosecond transient absorption techniques. A strong quenching of the fluorescence signal of FP1 was observed in both solvents, in comparison to the fluorescence of bis (pyropheophorbide a) (P2). This quenching is due to an intramolecular photoinduced electron transfer from the pyropheophorbide a (pyroPheo) moiety to the fullerene C₆₀ monoadduct. In DMF the charge-separated (CS) state of FP1 has a lifetime of 0.32 ns and undergoes a direct transition to the ground state, resulting in a very low value of photosensitised singlet oxygen generation. In toluene, energy transfer from the first excited triplet state of pyroPheo, which has been populated via relaxation of the CS state, generates a considerable amount of singlet oxygen. The lifetime of the CS state in the nonpolar solvent was estimated to be 0.29 ns. It was also shown that in both DMF and toluene the first excited singlet state as well as the triplet state of the fullerene moiety in FP1 are not occupied. PACS 31.70.Dk; 31.70.Hq; 33.50.-j; 34.70.+e     

In search of the dark state of 5-methyl-2-hydroxypyrimidine using a numerical DFT/MRCI gradient

In a recent publication, Lobsiger et al. [Phys. Chem. Chem. Phys. 12, 5032 (2010)] presented infrared and electronic absorption spectra of supersonic jet-cooled 5-methyl-2-hydroxypyrimidine (5M2HP), the enol form of deoxythymine. In addition, they reported on the fast nonradiative decay of the S₁ population to a dark state. In the present paper, we have investigated the mechanism and rate constants of this nonradiative decay by means of quantum chemical multi-configuration methods. To this end, minima of the lowest excited singlet and triplet states as well as the minimum-energy crossing point of singlet and triplet potential energy hypersurfaces (PEHs) have been determined employing a numerical DFT/MRCI gradient where DFT/MRCI stands for a combination of density functional theory (DFT) and a semi-empirical multi-reference configuration interaction (MRCI) approach. Rate constants have been calculated in the Condon approximation using a time-dependent approach based on harmonic oscillator functions and electronic spin–orbit coupling matrix elements evaluated at the DFT/MRCI level. It is shown that the first excited triplet state possesses ³(n?→?π*) character in the gas phase. Fast intersystem crossing is mediated by the low-lying ³(π?→?π*) state whose PEH crosses both, the S₁ ¹(n?→?π*) and T₁ ³(n?→?π*) PEHs.     

The role of spin-orbit coupling and hyperfine coupling in optical pumping ofF-centres

Optical pumping experiments onF-centres in potassium halides are described. The ground state polarization of the electronic spins achieved by optical pumping of isolatedF-centres is strongly dependent on the magnetic field and the wave-length of the pumping light. Experimentally it does not show the simple relationship to the magnetic circular dichroism (MCD) that has generally been assumed. A closer theoretical analysis shows indeed that the phenomena depend critically on the kind of spin mixing that prevails in the pumping cycle.If spin orbit coupling in the absorption band is the dominant spin mixing mechanism the sign of the pumping effect will be the same everywhere in the absorption band, if some other mechanism like spin mixing by radiationless transitions or hyperfine coupling to the surrounding nuclear spins prevails, the sign will follow the MCD. In strong magnetic fields experiments argue in favour of the first alternative, in low fields spin mixing by hyperfine coupling becomes important. On this basis the mechanism of optical pumping ofF-centres is discussed, and rate equations are given.