Local structure of titanium pair centers in SrF2 crystals: EPR and ENDOR spectroscopic studies

The local structure of titanium pair centers in SrF₂: Ti crystals is investigated using electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. It is found that titanium pair centers with spin moment S=2 and tetragonal symmetry of the magnetic properties are formed in SrF₂: Ti cubic crystals under certain growth conditions and during annealing. The tensor components of the fine and ligand hyperfine structures in the EPR and ENDOR spectra are determined. A model of the Ti⁺-Ti³⁺ paramagnetic dimer is proposed. This model provides an adequate interpretation of both the ferromagnetic nature of the exchange interaction and the observed displacements of four ligands in the first coordination sphere of titanium impurity ions in directions perpendicular to the impurity ion-ligand bonds.     

EPR and ENDOR Investigation of Rhodosemiquinone in Bacterial Reaction Centers Formed by B-Branch Electron Transfer

In photosynthetic bacteria, light-induced electron transfer takes place in a protein called the reaction center (RC) leading to the reduction of a bound ubiquinone molecule, Q_B, coupled with proton binding from solution. We used electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) to study the magnetic properties of the protonated semiquinone, an intermediate proposed to play a role in proton coupled electron transfer to Q_B. To stabilize the protonated semiquinone state, we used a ubiquinone derivative, rhodoquinone, which as a semiquinone is more easily protonated than ubisemiquinone. To reduce this low-potential quinone we used mutant RCs modified to directly reduce the quinone in the Q_B site via B-branch electron transfer (Paddock et al. in Biochemistry 44:6920–6928, 2005). EPR and ENDOR signals were observed upon illumination of mutant RCs in the presence of rhodoquinone. The EPR signals had g values characteristic of rhodosemiquinone (g _x  = 2.0057, g _y  = 2.0048, g _z  ~ 2.0018) at pH 9.5 and were changed at pH 4.5. The ENDOR spectrum showed couplings due to solvent exchangeable protons typical of hydrogen bonds similar to, but different from, those found for ubisemiquinone. This approach should be useful in future magnetic resonance studies of the protonated semiquinone.     

Tailored Nitroxide Radicals and Biradical Containing <Superscript>13</Superscript>C Enriched Acetylene Groups: ENDOR and DFT Investigation

A specially synthesized nitroxide biradical R₅-C≡¹³C-(p-C₆H₄)₂-¹³C≡C-R₅ (B4) and two radicals, R₅-C≡¹³CH (RCC) and R₅-C≡¹³C-C₆H₅ (RCCPh), where R₅ is 1-oxyl-2,2,5,5-tetramethyl-pyrroline group, have been studied by X- and W-band electron paramagnetic resonance (EPR) spectroscopy, and by W-band electron-nuclear double resonance (ENDOR). Spin density distribution and hyperfine splitting (hfs) constants on ¹³C atoms were experimentally determined and also calculated using ORCA 3.0.3 program package. The biradical and radicals geometries were optimized on UKS/B3LYP/cc-pVDZ level. Hfs constants were calculated using density functional theory (DFT) with PBE0 functional and N07D, and were compared with the experimental value of the hfs constant on ¹³C atoms, measured from ENDOR spectra. It is concluded that at small values of the exchange integral as J ≤ a/2 ≈ 7–8 G, the current quantum chemical approaches do not allow determining precise values of the hfs constants on the ¹³C atoms in the bridge connecting two paramagnetic nitroxide rings of the biradical.     

Alteration of the Axial Met Ligand to Electron Acceptor A0 in Photosystem I: Effect on the Generation of P 700 ·+ A 1 ·− Radical Pairs as Studied by W-band Transient EPR

Photosystem I (PS I) mutants from the cyanobacterium Synechocystis sp. PCC 6803 bearing point mutations to the axial ligands of A_0A (M688N_PsaA) and A_0B (M668N_PsaB) were studied by high-field W-band electron paramagnetic resonance (EPR) spectroscopy. It was found that the EPR observables of PS I from the M668N_PsaB mutant were virtual identical to that of the wild type (WT), and are clearly distinct from the M688N_PsaA mutant. In particular, the P ₇₀₀ ^·+ decay kinetics in the M688N_PsaA mutant is significantly slower than in the WT or the M668N_PsaB mutant. The analysis of the out-of-phase electron–electron dipolar electron spin echo envelope modulation shows that in the M668N_PsaB mutant, the estimated distance of 26.0 ± 0.3 Å agrees well with the 25.8 Å distance for the P ₇₀₀ ^·+ A _1A ^·? radical pair measured in the X-ray crystal structure. In the M688N_PsaA mutant, two populations are found with estimated distances of 26.0 ± 0.3 and 25.0 ± 0.3 Å in a ratio of 0.7–0.3, which agree well with the 25.8 Å distance for the P ₇₀₀ ^·+ A _1A ^·? radical pair and the 24.6 Å distance for the P ₇₀₀ ^·+ A _1B ^·? radical pair measured in the X-ray crystal structure. The data confirm that under the experimental conditions employed in this work, which involve dark-adapted samples without the pre-reduction of the iron–sulfur clusters, electron transport in cyanobacterial PS I is asymmetrical at 100 K, with the majority of electron transfer taking place through the A-branch of cofactors.     

ELDOR-detected NMR at Q-Band

In recent years, electron–electron double resonance detected nuclear magnetic resonance (EDNMR) has gained considerable attention as a pulsed electron paramagnetic resonance technique to probe hyperfine interactions. Most experiments published so far were performed at W-band frequencies or higher, as at lower frequencies detection of weakly coupled low-γ nuclei is hampered by the presence of a central blind spot, which occurs at zero frequency. In this article we show that EDNMR measurements and a meaningful data analysis is indeed possible at intermediate microwave frequencies (Q-band, 34 GHz), once experimental parameters have been optimized. With highly selective detection pulses and Gaussian shaped electron–electron double resonance (ELDOR) pulses it is possible to detect low-γ nuclei coupled to paramagnetic Mn²⁺. Weakly coupled ¹⁴N resonances, which are separated from the zero frequency by only 2.8 MHz, were readily detected. In systems where different spin active nuclei are coupled to the electron spin, particular care has to be taken when using higher powered ELDOR pulses, as combination frequencies from the two nuclei (?m _S = ±1, ?m _I,1 = ±1, ?m _I,2 = ±1) can lead to severe line broadening and complicated EDNMR spectra. We also compare the EDNMR spectra of ¹³C-labeled Mn–DOTA to ¹³C-Mims electron–nuclear double resonance to get a better insight into the similarities and differences in the results of the two techniques for ¹³C hyperfine coupling.     

Electron paramagnetic resonance and electron nuclear double resonance of NaCl:Rh2+: A comparison between similarly doped Bridgman- and solution-grown single crystals

In a recent electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) study several new rhodium related centres in a Bridgman-grown crystal were reported. For two centres a detailed microscopic model was established. The primary Rh²⁺ centre was identified as a [RhCl₆]^4? complex with a single charge compensating Na⁺ vacancy in a next nearest neighbour position. A second centre was identified as a rhodium dimer. Two other Rh²⁺ centres, with apparent axial symmetry, remained unidentified. In the present study a detailed comparison between Rh²⁺ defects in Bridgman- and solution-grown NaCl crystals is presented. One of the previously unidentified Rh²⁺ centres is shown not to be axial but to have orthorhombic-I symmetry and is identified as a cis-[RhCl₆]^4? complex with two next nearest neighbour Na⁺ vacancies. For the primary centre additional ENDOR interactions confirm the model mentioned above. Finally a comparison is made between the temperature stability of the primary and orthorhombic-I centre in Bridgman-grown and similarly doped solution-grown NaCl crystals.     

Applications of pulsed ELDOR-detected NMR measurements to studies of photosystem II: Magnetic characterization of YD tyrosine radical and Mn2+ bound to the high-affinity site

The pulsed electron-electron double resonance (ELDOR)-detected nuclear magnetic resonance (NMR) technique has been applied to the investigation of the hyperfine structure of the oxidized radical of Y_D tyrosine (Y _D ^· ) and Mn²⁺ ion bound to the high-affinity site in photosystem II. The resulting ELDOR spectrum of Y _D ^· was found to correspond with the pulsed electron-nuclear double resonance (ENDOR) spectrum except for a slightly larger linewidth (by a factor of 1.7). The spectrum showed marked anisotropy and revealed three peaks which can be assigned to matrix protons, C-3 and ?5 protons and one of the β-protons in the tyrosine molecule. The results demonstrate that the pulsed ELDOR-detected NMR technique is applicable to the study of organic radicals in biological systems. The Mn²⁺ ion bound to the high-affinity site in photosystem II yielded well-resolved ELDOR signals spreading over ±1000 MHz. The magnetic properties of the Mn²⁺ were characterized on the basis of the calculation of the ENDOR transitions and the anisotropy of the ELDOR spectrum.     

Self-Trapped Excitons in Ionic-Covalent Silver Halide Crystals and Nanostructures: High-Frequency EPR, ESE, ENDOR and ODMR Studies

Silver halides have unique features in solid state physics because their properties are considered to be of borderline nature between ionic and covalent bonding. In AgCl, the self-trapped hole (STH) is centered and partly trapped in the cationic sublattice, forming an Ag²⁺ ion inside of a (AgCl₆)^4? complex as a result of the Jahn–Teller distortion. The STH in AgCl can capture an electron from the conduction band forming the self-trapped exciton (STE). Recent results of a study of STE by means of high-frequency electron paramagnetic resonance, electron spin echo, electron–nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) are reviewed. The properties of the STE in AgCl crystals, such as exchange coupling, the ordering of the triplet and singlet sublevels, the dynamical properties of the singlet and triplet states, and the hyperfine interaction with the Ag and Cl (Br) nuclei are discussed. Direct information about the spatial distribution of the wave function of STE unpaired electrons was obtained by ENDOR. From a comparison with the results of an ENDOR study of the shallow electron center and STH, it is concluded that the electron is mainly contained in a hydrogen-like 1s orbital with a Bohr radius of 15.1 ± 0.6 Å, but near its center the electron density reflects the charge distribution of the hole. The hole of the STE is virtually identical to an isolated STH center. For AgCl nanocrystals embedded into the KCl crystalline matrix, the anisotropy of the g-factor of STE and STH was found to be substantially reduced compared with that of bulk AgCl crystals, which can be explained by a considerable suppression of the Jahn–Teller effect in nanoparticles. A study of ODMR in AgBr nanocrystals in KBr revealed spatial confinement effects and allowed estimating the nanocrystal size from the shape of the ODMR spectra.     

A DFT,X- and W-band EPR and ENDOR Study of Nitrogen-Centered Species in (Nano)Hydroxyapatite

Incorporation of the nitrogen-containing impurities in hydroxyapatite (HAp) powders with the sizes of the crystallites of (20–50) nm was studied using first-principles modeling combined with the multi-frequency (9 and 94 GHz) electron paramagnetic resonance (EPR) methods. It is shown that the observed EPR spectra are undoubtedly due to the presence of the bulk radiation-induced NO₃ ^2? radicals. This conclusion is based on spin-polarized density functional theory calculations of spectroscopic parameters within gauge-including projector augmented wave framework followed by the exact comparison of the simulated EPR and electron–nuclear double resonance spectra with the experimental findings. In addition, a comprehensive analysis of the simulated properties allows us to suggest that the paramagnetic centers preferably occupy PO₄ ^3? sites in the HAp structure.     

Electron nuclear quadruple resonance for assignment of overlapping spectra

Multiple resonance methods are important tools in EPR for revealing the network of hyperfine levels of free radicals and paramagnetic centers. The variations of electron nuclear double resonance (ENDOR) or electron spin-echo envelope modulation (ESEEM) techniques help to correlate nuclear frequencies with each other. These methods have limited utility when there is extensive overlap or suspected overlap in the EPR spectrum between different species or different orientations. In the ENDOR spectrum, overlap and second-order shifts of lines also leads to ambiguity in assignment and interpretation. A new electron nuclear multiple resonance method is presented here that is based on population transfer ENDOR. It is a quadruple resonance method that correlates ENDOR lines and reveals the network of hyperfine levels in samples with unoriented paramagnetic species and in samples with overlapping EPR or ENDOR lines.     

Anomalous Phases in Cavity-Free 240 GHz Pulsed ENDOR Spectra of 1.44 GeV Xe-Irradiated LiF

Paramagnetic centers generated by swift heavy ion irradiation of LiF crystals could be identified as electrons trapped at regular anion vacancy sites (F centers). Well-resolved electron-nuclear double resonance (ENDOR) spectra resulting from the hyperfine interaction with ⁷Li and ¹⁹F nuclei located in six different shells could be recorded. In order to preserve the millimeter-sized crystals, a cavity-free setup was used for the ENDOR experiments at an electronic Larmor frequency of 240 GHz. Apparently even under conditions of extremely high local energy loss in the ion track, the local density of persistent F centers is still sufficiently low to prevent distortions of the ionic crystal. The spread of hyperfine coupling constants was less than 5 %. Neither in electron paramagnetic resonance (EPR) nor in ENDOR spectra there was evidence for different types of paramagnetic centers. When performing ENDOR by applying the radiofrequency pulse directly after the 3-pulse Mims-type microwave sequence, an anomalous ENDOR effect was observed. The observed “positive” and “negative” ENDOR response can be attributed to efficient hole and anti-hole formation in the inhomogeneously broadened EPR spectrum and can be used to determine the sign of hyperfine coupling constants.     

Investigation of the Stationary and Transient A 1 ·− Radical in Trp → Phe Mutants of Photosystem I

Photosystem I (PS I) contains two symmetric branches of electron transfer cofactors. In both the A- and B-branches, the phylloquinone in the A₁ site is π-stacked with a tryptophan residue and is H-bonded to the backbone nitrogen of a leucine residue. In this work, we use optical and electron paramagnetic resonance (EPR) spectroscopies to investigate cyanobacterial PS I complexes, where these tryptophan residues are changed to phenylalanine. The time-resolved optical data show that backward electron transfer from the terminal electron acceptors to P₇₀₀^·+ is affected in the A- and B-branch mutants, both at ambient and cryogenic temperatures. These results suggest that the quinones in both branches take part in electron transport at all temperatures. The electron-nuclear double resonance (ENDOR) spectra of the spin-correlated radical pair P₇₀₀^·+A₁^·− and the photoaccumulated radical anion A₁^·−, recorded at cryogenic temperature, allowed the identification of characteristic resonances belonging to protons of the methyl group, some of the ring protons and the proton hydrogen-bonded to phylloquinone in the wild type and both mutants. Significant changes in PS I isolated from the A-branch mutant are detected, while PS I isolated from the B-branch mutant shows the spectral characteristics of wild-type PS I. A possible short-lived B-branch radical pair cannot be detected by EPR due to the available time resolution; therefore, only the A-branch quinone is observed under conditions typically employed for EPR and ENDOR spectroscopies.     

EPR Study of γ-Irradiated UHMWPE Doped with Vitamin E: Assessment of Thermal Effects on the Organic Radicals During Vitamin E Diffusion

Thermal effects on ultra-high-molecular-weight polyethylene (UHMWPE) residual radicals during the vitamin E diffusion process were studied in detail. Electron paramagnetic resonance (EPR) technique showed a significant reduction in concentrations of radiation-induced primary (alkyl (–CH₂– ^?CH–CH₂–), allyl (–CH₂–^?CH=CH–CH–CH₂–) and polyenyl (–^?CH–[CH=CH–] _m –) with m > 3) radicals for both control and vitamin E-doped samples. The concentrations of radiation-induced primary radicals (RIPRs) were found to decrease proportionally with the heat/diffusion time. While the EPR spectra of the control samples showed only polyethylene (PE) radicals, the spectra of vitamin E-doped samples were found to exhibit vitamin E radicals in addition to PE radicals. Of particular interest, the heat involved during vitamin E diffusion plays a significant role in reducing the radiation-induced primary radicals of UHMWPE. For 120 min of heat/diffusion time, the available quantity of primary radicals in control samples were found to be ~7.5 % of initial radicals. The leftover amounts of these primary radicals for vitamin E-doped samples were approximately ~10.0 %. In addition to this, EPR power saturation techniques were also used to assess the effects of initial heat/diffusion treatment on the oxygen-induced residual radicals (OIRRs): R₁ (–^?CH–[CH=CH–] _m –) with m > 3 and R₂ (^?OCH–[CH=CH–] _m –) with m = 2 or 3. It was found that the concentration of OIRRs also decreases proportionally with initial heat/diffusion time. The remaining amount of OIRRs relative to leftover RIPRs after heat/diffusion was found to be approximately 4.0 % in controls and was still found to be 10.0 % in vitamin E-doped UHMWPE. This may indicate that vitamin E slows down the oxidation processes, which may contribute to the strong oxidation resistance of vitamin E-doped UHMWPE.     

CW EPR, echo-detected EPR, and field-step ELDOR study of molecular motions of nitroxides ino-terphenyl glass: Dynamical transition, dynamical heterogeneity and β-relaxation

Continuous-wave electron paramagnetic resonance (CW EPR), echo-detected (ED) EPR, and field-step electron-electron double resonance (FS ELDOR) were simultaneously applied to study molecular motions of nitroxide spin probes of two different types in glassyo-terphenyl. A strong linear temperature dependence of the overall splitting of the CW EPR lineshape was found for nitroxide Tempone and only a weak one for a phenyl-ring-containing imidasoline nitroxide. The linear temperature dependence of the splitting is explained within the model of harmonic librations. The assessed libration frequency for Tempone is of the order of 3·10¹² rad/s. The observed remarkable difference between the two nitroxides is explained by the different strength of interactions between guest and host molecules and by dynamical heterogeneity of the glass. The nonlinear temperature dependence above 250 K is attributed to the onset of anharmonic motion that is postulated in a number of neutron scattering and Mössbauer spectroscopy studies for molecular glasses and proteins (the so-called dynamical transition). Above 245 K also ED EPR spectra change drastically, which may be explained on the same ground. Magnetization transfer was observed in FS ELDOR for nitroxide Tempone, with a time constant around 10^?5 s. It was found to be almost temperature-independent between 160 K and 265 K and was attributed to the Johari-Goldstein β-relaxation process. For the phenyl-ring-containing imidasoline nitroxide this transfer was not observed, which may be explained again by the dynamical heterogeneity of the glass and by small effectivity of the β-relaxation process in this case.     

A 236 GHz Fe3+ EPR Study of Nanoparticles of the Ferromagnetic Room-Temperature Semiconductor Sn1−x Fe x O2 (x = 0.005)

High-frequency (236 GHz) electron paramagnetic resonance (EPR) studies of Fe³⁺ ions at 255 K are reported in a Sn_1?x Fe _x O₂ powder with x = 0.005, which is a ferromagnetic semiconductor at room temperature. The observed EPR spectrum can be simulated reasonably well as the overlap of spectra due to four magnetically inequivalent high-spin (HS) Fe³⁺ ions (S = 5/2). The spectrum intensity is calculated, using the overlap I(BL) + (I(HS1) + I(HS2) + I(HS3) + I(HS4)) × exp(?0.00001B), where B is the magnetic field intensity in Gauss, I represents the intensity of an EPR line (HS1, HS2, HS3, HS4), and BL stands for the baseline (the exponential factor, as found by fitting to the experimental spectrum, is related to the Boltzmann population distribution of energy levels at 255 K, which is the temperature of the sample in the spectrometer). These high-frequency EPR results are significantly different from those at X-band. The large values of the zero-field splitting parameter (D) observed here for the four centers at the high frequency of 236 GHz are beyond the capability of X-band, which can only record spectra of ions with much smaller D values than those reported here.     

High-field EPR, ENDOR and ELDOR on bacterial photosynthetic reaction centers

We report on recent 95 and 360 GHz high-field electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR) and pulsed electron-electron double resonance (PELDOR) studies of wild-type and mutant reaction centers (RCs) from the photosynthetic bacteriumRhodobacter sphaeroides. Taking advantage of the excellent spectral and temporal resolution of EPR at 95 and 360 GHz, the electron-transfer (ET) cofactors radical ions and spin-correlated radical pairs were characterized by theirg- and hyperfine-tensor components, their anisotropicT ₂ relaxation as well as by the dipolar interaction between P ₈₆₅ ^?+ Q _A ^?? radical pairs. The goal of these studies is to better understand the dominant factors determining the specificity and directionality of transmembrane ET processes in photosynthetic RC proteins. In particular, our multifrequency experiments elucidate the subtle cofactor-protein interactions, which are essential for fine-tuning the ET characteristics, e.g., the unidirectionality of the light-induced ET pathways along the A branch of the RC protein. By our high-field techniques, frozen-solution RCs of novel site-specific single and double mutants ofR. sphaeroides were studied to modulate the ET characteristics, e.g., even to the extent that dominant B branch ET prevails. The presented multifrequency EPR work culminates in first 360 GHz ENDOR results from organic nitroxide radicals as well as in first 95 GHz high-field PELDOR results from orientationally selected spin-polarized radical pairs P ₈₆₅ ^?+ Q _A ^?? , which allow to determine the full geometrical structure of the pairs even in frozen-solution RCs.     

Electron Paramagnetic Resonance and Electron Spin Echo Studies of Co2+ Coordination by Nicotinamide Adenine Dinucleotide (NAD+) in Water Solution

Co²⁺ binding to the nicotinamide adenine dinucleotide (NAD⁺) molecule in water solution was studied by electron paramagnetic resonance (EPR) and electron spin echo at low temperatures. Cobalt is coordinated by NAD⁺ when the metal is in excess only, but even in such conditions, the Co/NAD⁺ complexes coexist with Co(H₂O)₆ complexes. EPR spin-Hamiltonian parameters of the Co/NAD⁺ complex at 6 K are g _z  = 2.01, g _x  = 2.38, g _y  = 3.06, A _z  = 94 × 10^?4 cm^?1, A _x  = 33 × 10^?4 cm^?1 and A _y  = 71 × 10^?4 cm^?1. They indicate the low-spin Co²⁺ configuration with S = 1/2. Electron spin echo envelope modulation spectroscopy with Fourier transform of the modulated spin echo decay shows a strong coordination by nitrogen atoms and excludes the coordination by phosphate and/or amide groups. Thus, Co²⁺ ion is coordinated in pseudo-tetrahedral geometry by four nitrogen atoms of adenine rings of two NAD⁺ molecules.     

Angle-selective measurements of spin soliton in ladder polydiacetylene by pulsed 94 GHz EPR

Angle-selection experiments of a spin soliton in randomly oriented ladder polydiacetylene were carried out by pulsed electron paramagnetic resonance (EPR) at W-band. EPR measurement using 94 GHz microwaves increased the difference in the resonance field due tog anisotropy of the spin soliton to allow the orientation dependence of transient nutation, electron nuclear double resonance (ENDOR) and spin relaxations to be investigated. The shape of theg anisotropy-resolved nutation spectrum was discussed on the basis of the EPR transition moments and the differences between spin relaxation times. Reliable assignments of hyperfine couplings to the β protons (H_β) of the alkyl side chains were achieved with the support of W-band ENDOR measurements. No significant orientational dependence in theT ₁ andT ₂ processes was found in terms of isotropy of the H_β-hyperfine interaction.     

Electron Spin Echo of Photoinduced Spin-Correlated Polaron Pairs in P3HT:PCBM Composite

A variation of the electron spin echo (ESE) signal caused by laser pulse in a blend of [6,6]-phenyl C₆₁ butyric acid methyl ester and poly(3-hexylthiophene) (P3HT:PCBM) was detected. This variation was attributed to light-generated paramagnetic species in P3HT:PCBM blend, with non-equilibrium spin polarization. The echo-detected electron paramagnetic resonance (EPR) spectrum of these species closely resembles the time-resolved EPR spectrum of spin-correlated polaron pair PCBM^?/P3HT⁺ (Behrends et al. in Phys. Rev. B 85:125206, 2012) and was assigned to this pair. The characteristic times for polarization and coherence decay (9 ± 1 and 1.0 ± 0.2 μs, respectively) were measured for the PCBM^?/P3HT⁺ pair at 77 K. These times are long enough, which shows the possibility of the application of the ESE technique for studying spin evolution of light-generated charge transfer intermediates in composites of fullerenes and conductive polymers.     

EPR and Optical Absorption Study of Cr3+-Doped Dipotassium Tetrachloropalladate

X-band electron paramagnetic resonance (EPR) study of Cr³⁺-doped dipotassium tetrachloropalladate single crystal is done at liquid nitrogen temperature. EPR spectrum shows two sites. The spin-Hamiltonian parameters have been evaluated by employing hyperfine resonance lines observed in EPR spectra for different orientations of crystal in externally applied magnetic field. The values of spin-Hamiltonian and zero-field splitting (ZFS) parameters of Cr³⁺ ion-doped DTP for site I are: g _x  = 2.096 ± 0.002, g _y  = 2.167 ± 0.002, g _z  = 2.220 ± 0.002, D = (89 ± 2) × 10^?4 cm^?1, E = (16 ± 2) × 10^?4 cm^?1. EPR study indicates that Cr³⁺ ion enters the host lattice substitutionally replacing K⁺ ion and local site symmetry reduces to orthorhombic. Optical absorption spectra are recorded at room temperature. From the optical absorption study, the Racah parameters (B = 521 cm^?1, C = 2,861 cm^?1), cubic crystal field splitting parameter (Dq = 1,851 cm^?1) and nephelauxetic parameters (h = 2.06, k = 0.21) are determined. These parameters together with EPR data are used to discuss the nature of bonding in the crystal.