Dominant Relaxation Pathway Research Articles

A Competition among Three Ultrafast Photoinduced Events in Thiotropolone: Internal Conversion vs Intersystem Crossing vs ESIPT.

Gas phase excited-state quantum wavepacket dynamics simulations of the thiotropolone demonstrate the ultrafast triplet formation upon photoexcitation to the dipole-allowed S2 state. The dominant relaxation pathway of the S2-T4 intersystem crossing, facilitated by the strong spin-orbit coupling and narrow energy gap, competes with the S2 to S1/S3 internal conversion. The wavepacket populated in T4 via the former pathway decays to lower triplet states. Computed potential energy profiles suggest proton transfer via S2, which might compete with internal conversion and intersystem crossing. The nonadiabatic population transfer from the S2 to S1/S3 states enables proton transfer via the latter states, resulting in multiple proton transfer pathways. Experimental investigations are necessary to shed light on the complex ultrafast photodynamics of thiotropolone.

Excitation of NH Stretching Modes in Aromatic Molecules: o-Toluidine and α-Methylbenzylamine.

Selectively excited o-toluidine and α-methylbenzylamine have been studied with quasi-classical trajectory procedures to determine the extent and timescales of intramolecular energy flow. The initial excitation is in the stretching mode of the para-CH bond, and its flow is initiated by interaction with an argon atom. Energy flow to the NH stretching mode is the dominant relaxation pathway, and its effectiveness is enhanced strongly by the methyl-NH interaction. Energy flow characteristics in both molecules are similar, but the flow is more effective in o-toluidine than in α-methylbenzylamine because the methyl group bonded to the benzene ring exerts stronger perturbation on the energy-flow pathway than the group bonded to the side chain. The relaxation of the initially excited CH completes on a timescale of several picoseconds, but the main part of energy flow to the NH occurs on a subpicosecond scale. In o-toluidine, carbon-carbon overtone modes lead to ring-CC bonds gaining and transporting more energy than high-frequency CH bonds, but they all gain far less energy than the NH stretching mode.

Controlling relaxation dynamics of excitonic states in monolayer transition metal dichalcogenides WS2 through interface engineering

Transition metal dichalcogenides (TMDs) are known to support complex excitonic states. Revealing the differences in relaxation dynamics among different excitonic species and elucidating the transition dynamics between them may provide important guidelines for designing novel excitonic devices. Combining photoluminescence and reflectance contrast measurements with ultrafast pump-probe spectroscopy at cryogenic temperatures, we herein study the relaxation dynamics of neutral and charged excitons in a back-gate-controlled monolayer device. Pump-probe results reveal quite different relaxation dynamics of excitonic states under different interfacial conditions: while neutral excitons have a much longer lifetime than trions in monolayer WS2, the opposite is true in the WS2/hexagonal boron nitride (h-BN) heterostructure. It is found that the insertion of the h-BN layer between the TMD monolayer and the substrate has a great influence on the lifetimes of different excitonic states. The h-BN flakes can not only screen the effects of impurities and defects at the interface but also help establish a non-radiative transition from neutral excitons to trions to be the dominant relaxation pathway, at cryogenic temperature. Our findings highlight the important role that the interface may play in governing the transient properties of carriers in 2D semiconductors and may also have implications for designing light-emitting and photo-detecting devices based on TMDs.

Electron transfer in photoexcited pyrrole dimers.

Following on from previous experimental and theoretical work [Neville et al., Nat. Commun. 7, 11357 (2016)], we report the results of a combined electronic structure theory and quantum dynamics study of the excited state dynamics of the pyrrole dimer following excitation to its first two excited states. Employing an exciton-based analysis of the Ã(π3s/σ*) and B̃(π3s/3p/σ*) states, we identify an excited-state electron transfer pathway involving the coupling of the Ã(π3s/σ*) and B̃(π3s/3p/σ*) states and driven by N-H dissociation in the B̃(π3s/3p/σ*) state. This electron transfer mechanism is found to be mediated by vibronic coupling of the B̃ state, which has a mixed π3s/3p Rydberg character at the Franck-Condon point, to a high-lying charge transfer state of the πσ* character by the N-H stretch coordinate. Motivated by these results, quantum dynamics simulations of the excited-state dynamics of the pyrrole dimer are performed using the multiconfigurational time-dependent Hartree method and a newly developed model Hamiltonian. It is predicted that the newly identified electron transfer pathway will be open following excitation to both the Ã(π3s/σ*) and B̃(π3s/3p/σ*) states and may be the dominant relaxation pathway in the latter case.

Spontaneous-relaxation-rate suppression in cavities with PT symmetry

We compute the spontaneous relaxation rate of a two-level atom in a planar cavity with parity ($\mathcal{P}$) and parity-time ($\mathcal{PT}$) symmetry. We find that at the center of a $\mathcal{PT}$-symmetric cavity the evanescent contribution to the relaxation rate is greatly suppressed. As this is the dominant relaxation pathway for cavities smaller than the transition wavelength, $\mathcal{PT}$-symmetric microcavities are able to suppress the spontaneous relaxation rate dramatically and, in some cases, reduce it to below the free-space level. The ability to reduce the relaxation rate and lengthen the excited-state lifetime has many applications in quantum control and can, for example, be used to increase atomic trapping times, improve photonic storage, and help maintain the coherence of atomic qubits.

Photoinduced charge carrier dynamics and spectral band filling in organometal halide perovskites

In recent years, the solution-processed organic-inorganic perovskite solar cells have attracted considerable attention because of their advantages of high energy conversion efficiency, low cost, and easily processing. Organometallic halide perovskite solar cells have gradually demonstrated particular superior properties in energy field due to their excellent photoelectric properties. This has been triggered by the unprecedented increase in its overall power conversion efficiency reaching 23% in just a few years, and it is becoming a direct competitor against the existing leading technology silicon. In this paper, 5-AVA-doped organometal halide perovskite films, (5-AVA)<sub>0.05</sub>(MA)<sub>0.95</sub>PbI<sub>3</sub> and (5-AVA)<sub>0.05</sub>(MA)<sub>0.95</sub>PbI<sub>3</sub>/Spiro-OMeTAD, are prepared by the two-step method. The generation and recombination mechanism of charge carriers in two kinds of film samples are discussed in detail. The bivalent band structure of perovskite film material CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> is determined by ultraviolet-visible absorption spectra of perovskite film (5-AVA)<sub>0.05</sub>(MA)<sub>0.95</sub>PbI<sub>3</sub> and (5-AVA)<sub>0.05</sub>(MA)<sub>0.95</sub>PbI<sub>3</sub>/Spiro-OMeTAD. We investigate the photocarrier dynamics and band filling effects in these two organometal halide perovskite films by using femtosecond transient absorption spectroscopy. For (5-AVA)<sub>0.05</sub>(MA)<sub>0.95</sub>PbI<sub>3</sub>, the photoinduced bleach recovery at 760 nm reveals that band-edge recombination follows second-order kinetics, indicating that the dominant relaxation pathway is via the recombination of free electrons and holes. With regard to the perovskite film (5-AVA)<sub>0.05</sub>(MA)<sub>0.95</sub>PbI<sub>3</sub> and (5-AVA)<sub>0.05</sub>(MA)<sub>0.95</sub>PbI<sub>3</sub>/Spiro-OMeTAD, the signal is photoinduced absorption from 550 nm to 700 nm. As the delay time increases, the electrons and holes are recombined, which results in a red shift of absorption spectrum in (5-AVA)<sub>0.05</sub>(MA)<sub>0.95</sub>PbI<sub>3</sub>. This can be referred to as Moss-Burstein band filling model. In contrast, the electrons and holes of (5-AVA)<sub>0.05</sub>(MA)<sub>0.95</sub>PbI<sub>3</sub>/Spiro-OMeTAD perovskite film sample are separated after photoexcitation. The holes rapidly transfer to the hole transport layer of Spiro-OMeTAD. It will lead to an increase in sample absorbance and a rapid recovery of bleaching signals. Consequently, electron-hole recombination is no longer a dominant pathway to the relaxation of photocarriers and the band filling effect is not significant in the composite film. Our findings provide a valuable insight into the understanding of the charge carrier dynamics and spectral band filling in mixed perovskites. These results conduce to the understanding of the intrinsic photo-physics of semiconducting organometal halide perovskites with direct implications for photovoltaic and optoelectronic applications, and provide a reference for the future research of perovskite solar cells.

Dissociation dynamics of 3- and 4-nitrotoluene radical cations: Coherently driven C-NO2 bond homolysis.

Monosubstituted nitrotoluenes serve as important model compounds for nitroaromatic energetic molecules such as trinitrotoluene. This work investigates the ultrafast nuclear dynamics of 3- and 4-nitrotoluene radical cations using femtosecond pump-probe measurements and the results of density functional theory calculations. Strong-field adiabatic ionization of 3- and 4-nitrotoluene using 1500 nm, 18 fs pulses produces radical cations in the ground electronic state with distinct coherent vibrational excitations. In both nitrotoluene isomers, a one-photon excitation with the probe pulse results in NO2 loss to form C7H7+, which exhibits out-of-phase oscillations in yield with the parent molecular ion. The oscillations in 4-nitrotoluene with a period of 470 fs are attributed to the torsional motion of the NO2 group based on theoretical results showing that the dominant relaxation pathway in 4-nitrotoluene radical cations involves the rotation of the NO2 group away from the planar geometry. The distinctly faster oscillation period of 216 fs in 3-nitrotoluene is attributed to an in-plane bending motion of the NO2 and CH3 moieties based on analysis of the normal modes. These results demonstrate that coherent nuclear motions determine the probability of C-NO2 homolysis in the nitrotoluene radical cations upon optical excitation within several hundred femtoseconds of the initial ionization event.

The position of the N atom in the pentacyclic ring of heterocyclic molecules affects the excited-state decay: A case study of isothiazole and thiazole

The radiationless decay of the isothiazole and thiazole molecules in the gas phase is investigated by a combination of static MS-CASPT2 computations with dynamics simulations, and some deactivation pathways are identified leading from the lowest excited singlet (S1) state back to the electronic ground (S0) state. The dominant relaxation pathway of the excited isothiazole is found to involve out-of-plane ring deformation (ring puckering) at the C4=C5(H8)S1 moiety, while the excited-state decay of thiazole can proceed through the ring puckering and S1C2 bond cleavage pathways both of which happen at the S1C2(H6) = N3 moiety. On the basis of the calculation results, we suggest that both ring-puckering and ring-opening routes should play rather important roles in the photophysics and photochemistry of heterocyclic molecules, and the position of the N atom in the heterocyclic ring has an effect on the excited state deactivation.

Carrier Diffusion Lengths of over 500 nm in Lead-Free Perovskite CH3NH3SnI3 Films.

The dynamics of photoexcited lead-free perovskite films, CH3NH3SnI3, were studied using broadband transient absorption and time-resolved fluorescence spectroscopy. Similar to its lead analogue CH3NH3PbI3, we show that free carrier (electrons and holes) recombination is also the dominant relaxation pathway in CH3NH3SnI3 films. The slow hot carrier relaxation time is 0.5 ps. Long carrier diffusion lengths for electrons (279 ± 88 nm) and holes (193 ± 46 nm) were obtained from fluorescence quenching measurements. We also show that SnF2 doping in the CH3NH3SnI3 film effectively increases the fluorescence lifetime up to 10 times and gives diffusion lengths exceeding 500 nm. These results suggest that the photophysics of CH3NH3SnI3 perovskite are as favorable as those of CH3NH3PbI3, demonstrating that it is a promising nontoxic lead-free replacement for lead iodide perovskite-based solar cells.

Magnetic relaxations arising from spin-phonon interactions in the nonthermally activated temperature range for a double-decker terbium phthalocyanine single molecule magnet.

Magnetic relaxations arising from spin-phonon interactions for a magnetically diluted double-decker terbium phthalocyanine single molecule magnet, dil1, in the nonthermally activated temperature range have been investigated. While the relaxation time, τ, is independent of the external static magnetic field, H(dc), in the high temperature range, where linear relationships between -ln τ and T(-1) are observed in the Arrhenius plot, magnetic field dependences for τ are observed in the lower temperature range. The τ(-1) vs H(dc) plot at 12 K fits the quadric curve when H(dc) < 12 kOe, while linear relationships are observed in the τ(-1) vs T plots in the temperature range of 12-20 K. These results indicate that the direct process is the dominant magnetic relaxation pathway in the nonthermally activated temperature range, while the contribution from the Raman process, if any, is not observable. We emphasize in this paper that the contribution from the thermal relaxation processes and the quantum tunneling of magnetizations (QTMs) to the experimentally observed magnetic relaxations must be evaluated carefully in order to avoid confusion between the thermal and quantum-mechanical relaxation pathways.

Band filling with free charge carriers in organometal halide perovskites

Femtosecond transient absorption spectroscopy measurements indicate that the dominant relaxation pathway for excited states in perovskite materials is by recombination of free electrons and holes.

Vibrational Relaxation of Cyanate or Thiocyanate Bound to Ferric Heme Proteins Studied by Femtosecond Infrared Spectroscopy

Femtosecond vibrational spectroscopy was used to measure the vibrational population relaxation time (<TEX>$T_1$</TEX>) of different anions bound to ferric myoglobin (<TEX>$Mb^{III}$</TEX>) and hemoglobin (<TEX>$Hb_{III}$</TEX>) in <TEX>$D_2O$</TEX> at 293 K. The <TEX>$T_1$</TEX> values of the anti-symmetric stretching (<TEX>${\nu}_1$</TEX>) mode of NCS in the <TEX>$NCS^-$</TEX> bound to <TEX>$Mb^{III}$</TEX> (<TEX>$Mb^{III}$</TEX>NCS) and <TEX>$Hb_{III}$</TEX> (<TEX>$Hb_{III}$</TEX>NCS) in <TEX>$D_2O$</TEX> are <TEX>$7.2{\pm}0.2$</TEX> and <TEX>$6.6{\pm}0.2$</TEX> ps, respectively, which are smaller than that of free NCS. in <TEX>$D_2O$</TEX> (18.3 ps). The <TEX>$T_1$</TEX> values of the <TEX>${\nu}_1$</TEX> mode of NCO in the <TEX>$NCO^-$</TEX> bound to <TEX>$Mb^{III}$</TEX> (<TEX>$Mb^{III}$</TEX>NCO) and <TEX>$Hb_{III}$</TEX> (<TEX>$Hb_{III}$</TEX>NCO) in <TEX>$D_2O$</TEX> are <TEX>$2.4{\pm}0.2$</TEX> and <TEX>$2.6{\pm}0.2$</TEX> ps, respectively, which are larger than that of free <TEX>$NCO^-$</TEX> in <TEX>$D_2O$</TEX> (<TEX>$1.9{\pm}0.2$</TEX> ps). The smaller <TEX>$T_1$</TEX> values of the <TEX>${\nu}_1$</TEX> mode of the heme-bound NCS suggest that intramolecular vibrational relaxation (VR) is the dominant relaxation pathway for the excess vibrational energy. On the other hand, the longer <TEX>$T_1$</TEX> values of the <TEX>${\nu}_1$</TEX> mode of the heme-bound NCO suggest that intermolecular VR is the dominant relaxation pathway for the excess vibrational energy in the <TEX>${\nu}_1$</TEX> mode of <TEX>$NCO^-$</TEX> in <TEX>$D_2O$</TEX>, and that intramolecular VR becomes more important in the vibrational energy dissipation of the <TEX>${\nu}_1$</TEX> mode of NCO in <TEX>$Mb^{III}$</TEX>NCO and <TEX>$Hb_{III}$</TEX>NCO.

State-Dependent Rotational Diffusion of Tetracene in n-Alkanes. Evidence for a Dominant Energy Relaxation Pathway

We have investigated the rotational diffusion of tetracene in the n-alkanes octane through hexadecane. Emission from the S1 state was monitored following excitation to the S1 state or the S2 state. Our data show that fast, non-radiative relaxation from S2 to S1 gives rise to local heating in the immediate vicinity of the chromophore. This local heating effect exhibits a solvent aliphatic chain length dependence for solvents C11 and longer, where solvents with an even number of carbons behave differently than those with an odd number of carbons. These data shed light on the possible origin(s) of odd-even effects in n-alkanes and suggest that a dominant intermolecular relaxation pathway for excess vibrational energy involves the S1 chromophore ring breathing mode (ca. 1383 cm(-1)) and the solvent terminal methyl group rocking mode (1375 cm(-1)).

Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution

Time-resolved infrared (TR-IR) absorption spectroscopy in both the femtosecond and nanosecond time domain has been applied to examine the photolysis of benzoic acid in acetonitrile solution following either 267 nm or 193 nm excitation. By combining the ultrafast and nanosecond TR-IR measurements, both the excited states and the photofragments have been detected and key mechanistic insights were obtained. We show that the solvent interaction modifies the excited state relaxation pathways and thus the population dynamics, leading to different photolysis behavior in solution from that observed in the gas phase. Vibrational energy transfer to solvents dissipates excitation energy efficiently, suppressing the photodissociation and depopulating the excited S(2) or S(3) state molecules to the lowest T(1) state with a rate of ∼2.5 ps after a delayed onset of ∼3.7 ps. Photolysis of benzoic acid using 267 nm excitation is dominated by the formation of the T(1) excited state and no photofragments could be detected. The results from TR-IR experiments using higher energy of 193 nm indicate that photodissociation proceeds more rapidly than the vibrational energy transfer to solvents and C-C bond fission becomes the dominant relaxation pathway in these experiments as featured by the prominent observation of the COOH photofragments and negligible yield of the T(1) excited state. The measured ultrafast formation of T(1) excited state supports the existence of the surface intersections of S(2)/S(1), S(2)/T(2), and S(1)/T(1)/T(2), and the large T(1) quantum yield of ∼0.65 indicates the importance of the excited state depopulation to triplet manifold as the key factor affecting the photophysical and photochemical behavior of the monomeric benzoic acid.

Photoelectron spectroscopy of the model GFP chromophore anion

A photoelectron spectroscopy study of the anionic model chromophore of the green fluorescent protein is presented. From the photoelectron spectra taken at 3.496 eV, 4.62 eV, and 6.15 eV the vertical and adiabatic detachment energies are determined to be 2.8 ± 0.1 eV and 2.6 ± 0.2 eV, respectively. The vertical detachment energy is higher than the S1← S0 absorption maximum (2.57 eV) and indicates that the S1 state is bound with respect to electron detachment in the Franck-Condon region. The photoelectron spectrum taken at 6.15 eV, together with TD-DFT calculations, are used to assign a number of excited states in the neutral radical that correspond to electron loss from occupied orbitals in the anion. The photoelectron spectrum at 2.58 eV shows evidence for electrons formed by thermionic emission, suggesting that internal conversion is the dominant relaxation pathway following S1← S0 excitation.

Photophysics and reductive quenching reactivity of gadusol in solution

The photostability and photophysics of gadusol in aqueous solution has been studied. The photodecomposition quantum yields (ca. 4 × 10(-2) and 1 × 10(-4) at acidic and neutral pH, respectively) confirm the high photostability of the metabolite, independently of the presence of oxygen, under physiological conditions. The nature of the electronic transition of gadusol has been assigned as π→π* on the basis of the solvatochromic shifts of the UV absorption spectrum and the time-dependent density functional theory calculation of the vertical transition energies. The results from the photoacoustic calorimetry point to the rapid non-radiative decay as the dominant relaxation pathway of the excited species at pH 7, which is consistent with the proposed UV-sunscreening role of the molecule in the early atmosphere. Laser flash photolysis experiments probed that the ground state of the enolate form (gadusolate) undergoes electron transfer reactions with some triplet sensitizers in water or methanol solution. A rate constant of 2 × 10(8) M(-1) s(-1) has been determined for the quenching of rose bengal triplet state in water at pH 7. This reductive quenching reactivity may be considered as one of the underlying mechanisms that support the antioxidant capacity of gadusol in biological environments.

Excited-State Dynamics of Spiropyran-Derived Merocyanine Isomers

Merocyanine (MC) isomers that are formed after absorption of a UV photon by 1',3'-dihydro-1',3'-3'-trimethyl-6-nitrospiro[2H-1-benzopyran-2',2'-(2H)-indole] were studied. Several, predominantly TTC and TTT, merocyanine isomers are present in toluene solution ("T" and "C" indicate trans and cis conformations of the C-C bonds in the methine bridge). Excitation in the MC visible absorption band (at 490, 550, and 630 nm) with 100 fs laser pulses was used to study MC excited-state dynamics. Internal conversion on the picosecond time scale was found to be the dominant relaxation pathway. Excited-state isomerization reactions were also observed. Excitation at 630 nm (assigned to TTC isomer excitation) leads to formation of a third isomer (either CTC or CTT). Excitation at 490 nm (assigned to TTT isomer excitation) leads to more complex excited-state relaxation, including formation of two isomers: TTC (absorption at 600 nm) and CTC or CTT (absorption at 650 nm).

Synthesis and properties of red emitter Ru(II) complexes based on 6,6′-disubstituted-4,4′-bipyrimidine

Heteroleptic complexes [Ru(bpy) 2(R 2bpm)] 2+, where bpy = 2,2′-bipyridine and R 2bpm = 6,6′-diaryl-4,4′-bipyrimidine, have been synthesized and characterized, together with the homoleptic complex [Ru(R 2bpm) 3] 2+, in which R 2bpm = 6,6′-diphenyl-4,4′-bipyrimidine. The substituent aryl on the bipyrimidine has significant effects on the properties of these complexes as compared to the parent [Ru(bpy) 2(bpm)] 2+ complex. The complexes exhibit Ru-to-bpm charge transfer (CT) absorptions centered at about 540 nm and Ru-to-bpy CT absorptions centered at about 435 nm. The assignment of the low energy absorptions is supported by the relative ease of the reduction of the new complexes as compared to [Ru(bpy) 3] 2+. The new complexes exhibit a relatively intense emission at room temperature, with lifetimes in the 10–50 ns range, with the homoleptic species exhibiting the higher-energy (maximum at 724 nm) and the longest-lived ( τ = 48 ns) emission among the complexes. Luminescence lifetimes and quantum yields are governed by the energy gap law, indicating that direct deactivation to the ground state is the dominant relaxation pathway for 1– 6, while thermally activated processes are inefficient.

Paramagnetic NMR investigations of high-spin nickel(II) complexes. Controlled synthesis, structural, electronic, and magnetic properties of dinuclear vs. mononuclear species.

New dissymmetric tertiary amines (N(3)SR) with varying N/S donor sets have been synthesized to provide mono- and dinuclear complexes. Acetate ions are used to complete the octahedral coordination sphere around nickel(II) atom(s). The facile conversion of mononuclear to dinuclear systems can be controlled to produce either mono- or dinuclear complexes from the same ligand. The dinuclear complex a(BPh(4))(2) ([Ni(2)(N(3)SSN(3))(OAc)(2)](BPh(4))(2)) has been characterized in the solid state by X-ray diffraction techniques as solvate: a(BPh(4))(2).(1/2)[5(CH(3)OH).(CH(3)CN).(CH(3)CH(2)OH)]. The two Ni atoms are six-coordinated and bridged by a disulfide group and two bidentate acetates. Magnetic susceptibility reveals a weak ferromagnetic exchange interaction between the two Ni atoms with J = 2.5(7) cm(-1). UV-vis studies suggest that the six-coordinated structure persists in solution. The (1)H NMR spectrum of a(BPh(4))(2) exhibits sharp significantly hyperfine shifted ligand signals. A complete assignment of resonances is accomplished by a combination of methods: 2D-COSY experiments, selective chemical substitution, and analysis of proton relaxation data. Proton isotropic hyperfine shifts are shown to originate mainly from contact interactions and to intrinsically contain a small J-magnetic coupling and/or zero-field splitting contribution. A temperature dependence study of longitudinal relaxation times indicates that a very unusual paramagnetic Curie dipolar mechanism is the dominant relaxation pathway in these weakly ferromagnetically spin-coupled dinickel(II) centers. The mononuclear nickel(II) analogue exhibits extremely broader (1)H NMR signals and only partial analysis could be performed. These data are consistent with a shortening of electronic relaxation times in homodinuclear compounds with respect to the corresponding mononuclear species.

The tetranuclear manganese cluster in photosystem II: location and magnetic properties of the S2 state as determined by saturation-recovery EPR spectroscopy.

The spin-lattice relaxation enhancement of the dark-stable tyrosine radical, YD., by the S2 state of the O2-evolving complex (OEC) of photosystem II (PSII) has been measured by using saturation-recovery EPR spectroscopy. Two forms of the S2 state have been compared: the multiline EPR signal species in untreated PSII and the altered multiline EPR signal species in NH3-treated PSII. Previous work has shown that the non-single-exponential spin-lattice relaxation kinetics of YD. in S2-state PSII result from a dipole-dipole interaction with the Mn4 cluster of the OEC. By taking into account the temperature variation of the effective magnetic moment of the S2-state multiline EPR signal form of the OEC, we provide a quantitative analysis of its temperature-dependent enhancement of the spin-lattice relaxation of YD.. Different spin states of the Mn4 cluster in the S2 state are responsible for the effect at different temperature regimes: for T </= 10 K, it is the ground spin state (S = 1/2); for T >/= 30 K, it is the first excited spin state; and at intermediate temperatures, the contributions of the two spin states are comparable. The relaxation enhancement of YD. is equivalent for both forms of the S2-state multiline EPR signal examined, indicating that the magnetic properties of the Mn4 cluster are very similar in the S2 state for both untreated and NH3-treated PSII. EPR progressive microwave-power saturation has also been used to assess the spin-lattice relaxation properties of the Mn4 cluster giving the altered S2-state multiline EPR signal in the NH3 derivative of PSII. The Orbach mechanism is shown to provide the dominant relaxation pathway; the energy difference between the ground and first excited spin states is estimated to be 30 +/- 2 cm-1, which is very similar to the value found for the S2-state multiline EPR signal species in untreated PSII. Below 4 K, the effectiveness of the S2-state multiline EPR signal species as a spin relaxation enhancer of YD. drops dramatically. This is interpreted to occur because of temperature-dependent 55Mn nuclear spin-lattice relaxation which causes averaging of the effective Larmor frequency of the S2-state multiline EPR signal species during the time scale for spin-lattice relaxation of YD.; because the line shape of the S2-state multiline EPR signal is dominated by isotropic 55Mn nuclear hyperfine splittings, such nuclear relaxation processes allow frequencies in near resonance with that of YD. to be accessed, thereby producing a greater relaxation enhancement. By using a dipolar model that includes the line shapes of both the YD. and S2-state multiline EPR signals, the spin-lattice relaxation enhancement of YD. is analyzed to obtain a lower limit of 22 A for the distance between YD. and the OEC. Together with recent studies showing a close proximity of the Mn4 cluster to YZ., these results provide further support for an asymmetric location of the Mn4 cluster with respect to the two redox-active tyrosines in PSII.