Optical and time-resolved electron paramagnetic resonance studies of the excited states of para-methylcinnamic acid and para-methylcinnamate anion

Time-resolved electron paramagnetic resonance (EPR), fluorescence, and phosphorescence spectra have been observed for the excited states oftrans-p-methylcinnamic acid (p-MeCA) andtrans-p-methylcinnamate anion (p-MeCA^?) in rigid organic glasses at 77 K. With a stretched-polymer-film technique, we assigned the resonance fields in the time-resolved EPR spectra of the lowest excited triplet (T₁) states ofp-MeCA andp-MeCA^?. From the analysis of these spectra we concluded that the deviation from planar structure in the T₁ state is small inp-MeCA andp-MeCA^? and the direction of C=O iss-cis to the ethylenic C=C bond inp-MeCA. The deprotonation appears to have little effect on the zero-field splitting (ZFS) parameters. The ZFS parameters were calculated theoretically using semiempirical molecular orbitals. The sublevel preferentially populated by intersystem crossing (ISC) is T _y in bothp-MeCA andp-MeCA^?. However, following the deprotonation ofp-MeCA, (P _y?P _z)/(P _x?P _z) changes from 5.7 inp-MeCA to 2.1 inp-MeCA^? (P _i are relative populating rates; thex andy axes are close to the long and short in-plane molecular axes, respectively, andz-axis is perpendicular to the molecular plane). The fluorescence lifetimes indicate that the deprotonation has little effect on the sum of the three ISC rate constants for the three T₁ sublevels. A decrease in acidity ofp-MeCA upon excitation has been observed.     

Two-laser two-color time-resolved EPR study on higher-excited-state triplet-singlet intersystem crossing of porphyrins and phthalocyanines

Photoinduced effects on the electron spin polarization (ESP) in the lowest excited triplet (T₁) states of porphyrins (PORs) and phthalocyanines (PCs) have been observed with a two-color time-resolved (TR) electron paramagnetic resonance (EPR) technique in a glassy matrix at low temperatures. On single-color excitation with the wavelengths of the ground state absorptions of PORs and PCs, polarized EPR spectra due to the corresponding T₁ state were observed. The polarization patterns match well with interpretation as anisotropic intersystem crossing (ISC) induced by the spinorbit coupling between the singlet excited (S₁) and the triplet states. In contrast, two-color excitation led to a change of the phase of the T₁ state polarization pattern to the opposite. The observed ESP in the T₁ state resulting from the excitation to the upper triplet state (T _n ) was interpreted in terms of anisotropic ISC between the T _n and S₁ states. From the analysis of the ESP, changes in the quantum yields of the reverse ISC processes were determined at different temperatures. The results could be best interpreted by the existence of thermal pathways with small activation energy in the relaxation processes.     

Structures and electronic states of photoexcited states in a system of two nitroxide radicals linked to fullerene studied by two-dimensional pulsed nutation and time-resolved electron paramagnetic resonance spectroscopy

Magnetic properties of fulleropyrrolidine adducts with two stable nitroxide radicals (2,2,6,6-tetramethylpiperidine-1-oxyl, TEMPO) were studied in toluene solution by continuous-wave time-resolved (TR) and pulsed electron paramagnetic resonance (EPR) spectroscopy in the ground and photoexcited states. Four isomers of the bisadduct,trans-1,trans-2,trans-3, and equatorial forms, having the second pyrrolidine ring at different [6-6] bonds were synthesized. In the ground states, the exchange interaction between two TEMPOs is so small that the spin state of the bisadduct is a doublet in nature. By means of spectral simulations of the EPR spectra in frozen solution at 70 K, the upper limit of the exchange interaction was estimated to be 5 MHz for thetrans-1 andtrans-2 and 10 MHz for thetrans-3 and equatorial isomers. The simulation was also made to determine relative positions of the two TEMPO groups with respect to the pyrrolidine ring. Photoexcited states of the bisadducts with excitation of the 532 nm laser pulse were studied in frozen toluene solution at 5–100 K by using two-dimensional (2-D) pulsed nutation EPR and TREPR. The spin multiplicity of the excited state was determined by the nutation frequency. All of the four bisadducts showed strong exchange couplings between two TEMPOs and fullerene triplet³C ₆₀ ^* , resulting in the generation of the excited quintet and triplet states. The excited triplet states have been observed and assigned for the first time in strongly coupled triplet-radical systems. The zero-field splittings of the quintet state determined from the 2-D nutation EPR spectra were analyzed as the sum of the spinspin interactions among the three paramagnetic centers, two TEMPOs and³C ₆₀ ^* . On the basis of these analyses, the spin distribution on the³C ₆₀ ^* part and the geometry of two TEMPOs are discussed.     

Time-resolved EPR and ODMR studies on the lowest excited triplet states of α-silyl and α-germyl ketones

Sublevel properties of the lowest excited triplet (T¹) nπ* states of α-silyl and α-germyl ketones were examined by means of ODMR, time-resolved EPR and optical spectroscopy. The EPR parameters, D, E and g, population ratios, and triplet lifetimes were obtained. The D value and the triplet lifetime varied among the molecules. In contrast the E value and population ratio remains nearly the same. These properties together with their solvent dependence and emission properties are interpreted in terms of spin-orbit couplings between T₁ (nπ*) and higher S₁ (nπ*), T₂ (ππ*) and S₂ (ππ*) states. An origin of the remarkable red-shifts of ^1,3 (π*) are discussed based on a model of delocalized n, π and π* electrons over the Si and Ge atoms. This model is also consistent with all the triplet properties obtained.     

Time‐resolved spectroscopic and density functional theory investigation of the photochemistry of suprofen

The photochemistry of suprofen (SPF) was investigated by femtosecond transient absorption (fs‐TA), resonance Raman (RR) and nanosecond time‐resolved resonance Raman (ns‐TR³) spectroscopic methods to gain additional information so as to better elucidate the possible photochemical reaction mechanism of suprofen in several different solvents. In neat acetonitrile (MeCN), the fs‐TA and ns‐TR³ experimental data indicated that the lowest lying excited singlet state S₁ (nπ*) underwent an efficient intersystem crossing process (ISC) to the excited triplet state T₃ (ππ*), followed by an internal conversion (IC) process to T₁ (ππ*). In the aqueous solution, a triplet biradical species (³ETK‐1) was obtained as the product of a decarboxylation process from triplet suprofen anion (³SPF⁻) and the reaction rate of the decarboxylation process was determined by the concentration of H₂O. A protonation process for ³ETK‐1 leads to formation of a neutral species (³ETK‐3) that was directly observed by ns‐TR³ spectra, then this ³ETK‐3 species decayed via ISC process to generate final product. Copyright © 2014 John Wiley & Sons, Ltd.     

Electron-lattice interaction of Ag− and Cu− centers in alkali halides

Absorption, emission, and excitation spectra of Ag^? centers in KCl, RbCl, CsCl, and CsBr are measured at low temperatures. The positions of theA emission bands are slightly different afterC andA band excitation, respectively. This is believed to be due to the existence of two different types of minima in the adiabatic potential energy surface of the³ T _1u state. The symmetry of the energy minima in the¹ T _1u state is trigonal for KCl∶Ag^? and Cu^?, but tetragonal for CsBr∶Ag^?. This becomes evident from the polarization properties of the emission. The energy and temperature dependence of the polarization is discussed. Uniaxial stress causes polarized emission of Ag^? and Cu^? centers measured from LHeT to 100 K. This is due to a splitting and mixing of the relaxed excited states by the stress. The effects are used to calculate the coupling constants between thep electron and theE _g andT _2g lattice modes. They are compared with predictions from the point-charge model for different lattice structures. A new assignment of the absorption bands of KCl∶Cu^? to the excited states of Cu^? is established on measurements of emission spectra and lifetimes.     

On theg-value shift and intersystem crossing in photo-excited radical-triplet systems

The electron paramagnetic resonance (EPR) signals of photoexcited quartet (Q₁) states for zinc(II) tetra-tert-butyl-phthalocyanine (ZnPc) ligated by 3- and 4-(N-nitronyl-nitroxide) pyridine radicals (3-NOPy, 4-NOPy) were observed in toluene solution at room temperature by means of X-band (9.4 GHz) time-resolved EPR (TREPR) spectroscopy. Theg values of Q₁ in the ZnPc-3-NOPy and ZnPc-4-NOPy complexes were found to beg=2.0025 andg=2.0036, respectively. The obtainedg value (2.0036) for ZnPc-4-NOPy is in good agreement with the value (g=2.0037) of the Q₁ state calculated under the strong-exchange limit. Theg value (2.0025) is just an average of the Q₁ and D₁ (g=2.0013) states for ZnPc-3-NOPy. Theg value of Q₁ for zinc(II) meso-tetraphenylporphine (ZnTPP) ligated by 3-NOPy showed a slight shift (g=2.0027) at X-band and no shift (g=2.0031) at W-band from the calculatedg value (g=2.0031) (J. Fujisawa, Y. Iwasaki, Y. Ohba, S. Yamauchi, K. Koga, S. Karasawa, M. Fuhs, K. Möbius, S. Weber, Appl. Magn. Reson. 21, 483–493, 2001). These changes in theg value were found to originate from an averaging of the TREPR spectra over the Q₁ and photoexcited doublet (D₁) states via a fast intersystem crossing (ISC) process. The ISC rates between these two states were estimated by means of numerical calculations with the modified Bloch equations as 1.2·10⁸ and 6·10⁷ s^?1 for the ZnTPP-3-NOPy complex at the X- and W-bands, respectively. The lower limit of the ISC rate was obtained as 10⁹s^?1 for the ZnPc-3-NOPy complex and the higher limit was found to be 3.1·10⁸ s^?1 for the ZnPc-4-NOPy complex.     

Rotational spectrum of trans-trans diethyl ether in the ground and three excited vibrational states

We report the results of a comprehensive reinvestigation of the rotational spectrum of diethyl ether based on broadband millimetre-wave spectra recently recorded at The Ohio State University and in Warsaw, covering the frequency region 108-366 GHz. The data set for the ground vibrational state of trans-trans diethyl ether has been extended to over 2000 lines and improved spectroscopic constants have been determined. Rotational spectra in the first excited vibrational states of the three lowest vibrational modes of trans-trans-diethyl ether, ν₂₀, ν₃₉, and ν₁₂ have been assigned. The v₂₀ = 1 and v₃₉ = 1 states are near 100 cm⁻¹ in vibrational term value and are coupled by a strong c-axis Coriolis interaction, which gives rise to many spectacular manifestations in the rotational spectrum. All of these effects have been successfully fitted for a dataset comprising over 3000 transitions, leading to precise determination of the energy difference between these states, (ΔE/hc)=10.400222(5) cm⁻¹. A newly developed software package for assignment and analysis of broadband spectra is described and made available.     

Synthesis and Structural, Magnetic and EPR Characterization of Discrete Finite Antiferromagnetic Chains

The synthesis, magnetic and electron paramagnetic resonance (EPR) characterisation of isolated, discrete, {Cr _n ^III } antiferromagnetically coupled chain complexes is reported for n = 6 and 7. Previous studies had reported supramolecular linked {Cr _n ^III } _x species. For n = 6, the lowest lying total spin state is diamagnetic with S = 1 and 2 first and second excited states, respectively; for n = 7, the lowest lying total spin state is S = 3/2 with S = 1/2 and 5/2 first and second excited states, respectively. The zero-field splittings of these states are well defined by low-temperature, multi-frequency EPR spectroscopy.     

Properties of the 3− first excited state in the doubly closed shell nucleus146Gd

Conversion electron measurements confirm the 3^? assignment recently proposed for the 1579 keV first excited state in¹⁴⁶Gd. Fromγγ- ande ^? γ-coincidence data the half life of that state has been determined asT _1/2=1.06±0.12 ns.     

Excitation of lowest electronic states of thymine by slow electrons

Excitation of lowest electronic states of the thymine molecules in the gas phase is studied by elec- tron energy loss spectroscopy. In addition to dipole-allowed transitions to singlet states, transitions to the lowest triplet states were observed. The low-energy features of the spectrum at 3.66 and 4.61 eV are identified with the excitation of the first triplet states 1₃ A′ (π → π*) and 1₃ A″ (n → π*). The higher-lying features at 4.96, 5.75, 6.17, and 7.35 eV are assigned mainly to the excitation of the π → π* transitions to the singlet states of the molecule. The excitation dynamics of the lowest states is studied. It is found that the first triplet state 1³ A′(π → π*) is most efficiently excited at a residual energy close to zero, while the singlet 2₁ A′(π → π*) state is excited with almost identical efficiency at different residual energies.     

Shifts of g Values in the Excited Triplet States of Metal Complexes Studied by Time-Resolved W-band EPR

A highly time-resolved high-frequency/high-field W-band electron paramagnetic resonance (EPR) (ν ~ 94 GHz) is a powerful technique to determine small g anisotropies of transient paramagnetic species. We applied this method to studies of the lowest excited triplet (T₁)³ ππ* states in metal complexes such as a platinum (Pt) diimine complex and metal (Zn and Mg) porphines in rigid glasses. From the analyses of time-resolved EPR spectra, g anisotropies were obtained as g _z  = 2.0048, g _x  = g _y  = 2.0035 for Pt(b-iq)(CN)₂ (b-iq = 3,3′bi-isoquinoline) and g _z  = 1.9968, g _x  = g _y  = 2.0022 for zinc tetraphenylporphine (ZnTPP). No measurable anisotropies were found for magnesium (Mg) TPP. The g values of the Pt complex are larger than g _e (=2.0023, g value of free electron) and that g _z of ZnTPP is smaller than g _e. These results were interpreted in terms of the nature of the perturbed states: the higher triplet ππ′* state mixes with T₁(ππ*) via spin–orbit coupling in ZnTPP. In contrast, the higher triplet dπ* state is involved in this coupling for the Pt complex. Thus, the nature of the perturbed state can be distinguished from the anisotropic g values of the T₁(ππ*) state.     

Quantitative time-resolved EPR CIDEP study of the photodecomposition oftrans-azocumene in solution

The cumyl radical system, which is created after laser flash irradiation oftrans-azocumene in benzene solution at room temperature, is investigated using time-resolved EPR spectroscopy. From the quantitative analysis of EPR time-profiles at different microwave powers the spin relaxation timesT ₁=3.5±0.3 μs andT ₂=2.5±0.1 μs are evaluated as well as the magnitude of the chemically induced electron polarization (CIDEP), which is generated by the radical pair mechanism (RPM). The geminate RPM polarization is found to be considerably smaller than the F-pair one, 32±2 and 48±5 in units of the Boltzmann polarization, respectively. This is attributed to an initial radical separation in the geminate pair, caused by the cleavage reaction. Besides cleavage, the photoexcitedtrans-azocumene also decays via isomerization to the thermally unstablecis-isomer, the lifetime of which is found to be 14±3 μs at 293 K in benzene, three times longer than in cyclohexane. The quantum yield of free radicals, escaping from the primary cage, is determined as 0.28±0.06 for the decay of the excitedtrans-azocumene and 0.18±0.04 for the thermal cleavage of thecis-isomer. The self-termination of cumyl radicals proceeds with a rate constant 2k _t=7±1)·10⁸ M^?1s^?1 in benzene at RT.     

In-beam study of high-spin states in199,200,201Po and systematical features of Z=84 polonium isotopes

Excited states in^199,200,201Po were populated in the reactions¹²C+¹⁹⁴Pt and¹²C+¹⁹⁵Pt. The subsequentγ-radiation was studied using conventional in-beam spectroscopic methods. States with spins up to (29/2), 18 and ≧35/2?, respectively, were populated in the three nuclides. Three isomeric states with the following half-lives were observed in²⁰⁰Po:T _1/2(8⁺)=90(15) ns,T _1/2(11^?)=120(20) ns andT _1/2(12⁺)=267(4) ns. The structure of the excited states was interpreted within the framework of the spherical shell model. The three isomers are suggested to be two-quasiparticle states with configurationsπ(h _{2 2})_8J, π(h₉i_13/2)₁₁- and v(i _{1 3/2 ?2})₁₂₊. A self-consistent Hartree-Fock calculation was performed to obtain ground-state deformations of the neighbouring Pb cores. From the results of the experiments and the calculations it was concluded that no appreciable deformations of the cores are manifested in the yrast states of these three Po nuclei.     

The deformation of the ground and excited states in the Ag and Sn nuclei

The microscopic calculation of the potential energies in the ground and excited states of Ag and Sn nuclei has been performed. The single particle Nilsson potential and the shell correction Strutinski method have been used. The weak sensitivness to nonaxial deformation has been found for even neighbours of these nuclei. The small tendency towards prolate deformation of the ground and excited one-quasiparticle states originating from theg _9/2 proton subshell in^101–105Ag odd isotopes has been noticed. The behaviour with quadrupole e and hexadecapole ε₄ deformation of the ground and two-quasiparticle excited 0⁺ states originating from thed _5/2,g _9/2 andg _7/2 proton subshells andh _11/2 neutron subshell in^112–118Sn has been investigated. The small quadrupole deformation of the excited 0⁺ states has been found what is in agreement with the experimental data concerning the rotational bands build on the first excited 0⁺ states in Sn isotopes.     

Lowest excited states of 2-aminopurine

Absorption and fluorescene spectra and quantum yields of emission over a wide range of pH and solvent polarity were measured for 2-aminopurine and 2-dimethylaminopurine. An increase in dipole moment and a rise of pK values for N₁(N₃) ring atom protonation in the excited state were demonstrated. Thus, the lowest excited singlet state shows partially the (1, a_π¹) configuration. The polarization, lifetimes and the phosphorescence-to-fluorescence ratios indicate that spin-orbit coupling of ¹(n, π¹) and ¹(1, a_π¹) with the lowest triplet state is the main source of phosphorescence intensity. The matrix element of spin-orbit coupling of ¹(n, π¹) to the T₁ state is about 33 times larger than that of ¹(1, a_π¹). The temperature- dependent process of 2-aminopurine fluorescence quenching in either is presumably due to the thermal population of the second excited triplets state of (n, π¹) configuration, which can approximately be located at 370 cm^-1 above the lowest (1, a_π¹) singlet.     

Studies of the temperature dependence of the phosphorescence spectra and decay rates of aromatic carbonyl molecules in mixed organic crystals

The temperature dependence of the phosphorescence spectra, decay rates and the S ₀ → T ₂(³ nπ*) absorption spectra were studied for aromatic carbonyl molecules in mixed organic crystals. The energy separation, ΔE_T , between the ³ ππ* lowest excited triplet (T ₁) states and the higher ³ π ^* states (T ₂) was estimated for several systems from the temperature dependence of the phosphorescence spectra and decay rates. It was found that the decay rates of the aromatic carbonyl molecules in the mixed crystal systems studied are determined by (1) thermal population to the ³ nπ* states and (2) increased radiationless transition rates at higher temperatures.     

Particle plus octupoleM2/E3 isomers and high-spin particle-hole states in147Tb and148Tb

The level structures of theN=82 andN=83 nuclei¹⁴⁷Tb and¹⁴⁸Tb have been studied by means of (α, 8n) and (α,7n) reactions induced by 68 to 110 MeVα particle bombardments of¹⁵¹Eu targets. In-beam conversion electron measurements have established that isomers withT _1/2=4.8(6)ns in¹⁴⁷Tb andT _1/2=22(1)ns in¹⁴⁸Tb decay byM2+E3 transitions to the ground states. The measuredB(E3) values show that the isomeric states arise from the coupling of the valence nucleon(s) to the¹⁴⁶Gd core octupole. Particlephonon coupling in these nuclei and in the one-neutron nucleus¹⁴⁷Gd is discussed and compared with well known cases involving the²⁰⁸Pb core. The higher lying yrast states in the two Tb nuclei are described as shell-model particle-hole excitations using empirical single particle energies and nucleon-nucleon interactions.     

A comparative spectroscopic investigation of21Ne and21F by pickup reactions

The reactions²²Ne(d, t)²¹Ne and²²Ne(d, τ)²¹F have been investigated in a parallel experiment atE _d=52MeV. Energy spectra of tritons andτ particles have been measured up to excitation energies of 18MeV in both²¹Ne and²¹F nuclei. Thel values could be determined, and spectroscopic factors have been obtained by a DWBA analysis of the measured angular distributions. Together with the results from a preceding \({}^{22}Ne(\vec d, \tau ){}^{21}F\) experiment, several spins could be determined in²¹F. From a comparison of the triton andτ particle spectra,T=3/2 states in²¹Ne could be identified and on this basis the new information on spins of²¹F states could be transferred to their analog states in²¹Ne. The completeT _< andT _> parts of the (2s, 1d) strengths could be observed. The 1p strength is highly fragmented. Of theT _< part only 60% of the 1p1/2 and 40% of the lp3/2 strength could be found, but the totalT _> part of the 1p strength could be localized. The spectroscopic results for positive parity states are in qualitatively good agreement with shell model predictions.     

Alpha decay properties of199Rn and199mRn

Theα-decays of¹⁹⁹Rn (E _α = (6.989±0.010) MeV,T _1/2>300ms) and of^199m Rn (E _α = (7.060±0.015) MeVT _1/2=(61 _?2 ⁺³² ) ms) were identified by anα-α-correlation method. They proceed via separated decay paths to¹⁹⁵Po and^195m Po, respectively. The spins of the involved states are discussed by aid of the shell model, and a tentative spin assignment is given.