Atomic Multiplet Calculations Research Articles

Precise dd excitations and commensurate intersite Coulomb interactions in the dissimilar cuprates YBa2Cu3O7–y and La2–xSrxCuO4

Using high-resolution extreme ultraviolet resonant inelastic X-ray scattering (EUVRIXS) spectroscopy at Cu M-edge, we observed the doping dependent spectral shifts of inter-orbital (dd) excitations of YBa_2Cu_3O_(7-x) and La_(2-x)Sr_xCuO_4. With increasing hole doping level from undoped to optimally doped superconducting compositions, the leading edge of dd excitations is found to shift towards lower energy loss in a roughly linear trend that is irrespective to the cuprate species. The magnitude of energy shift can be explained by including a 0.15 eV Coulomb attraction between Cu 3d_(x^2-y^2) electrons and the doped holes on the surrounding oxygens in the atomic multiplet calculations. The consistent energy shift between distinct cuprate families suggests that this inter-site Coulomb interaction energy scale is relatively material-independent, and provides an important reference point for understanding charge density wave phenomena in the cuprate phase diagram.

Theory of circular dichroism in angle-resolved resonant photoemission from magnetic surfaces

A theoretical method is presented for angle-resolved photoemission at the transition metal $L$-edge resonance. It combines atomic multiplet calculations for the second-order resonant photoemission amplitude on the core-level site and a single scattering calculation of the photoelectron final state. The theory is applied to a magnetized Ni(111) surface excited with circularly polarized x rays at the Ni ${L}_{2,3}$-edge resonance with a focus on the circular dichroism (CD) signal. Good agreement with available experimental data is achieved. It is shown that the CD pattern is composed of a slowly varying magnetic signal induced by the atomic resonant process and a signal of fast angular modulations that are due to the interference of primary and scattered waves, known as the Daimon effect. The two types of CD signals are found to be nearly additive. At the Ni ${L}_{2}$-edge resonance, the angular dependence of the magnetic CD is well described by a simple expression known from x-ray magnetic CD. At the ${L}_{3}$ edge, however, the angular dependence is more complex and shows a pronounced final state multiplet dependence. With the present theory, it becomes possible to extract element- and site-selective magnetic information of surfaces from the CD in angle-resolved resonant photoemission data.

Erbium and thulium on MgO(100)/Ag(100) as candidates for single atom qubits

Lanthanide atoms on surfaces are prospective platforms for realizing atomic-scale quantum logic units. Here, the authors combine scanning tunneling microscopy, x-ray magnetic circular dichroism, density functional theory, and atomic multiplet calculations to identify the quantum level structure of erbium and thulium atoms on MgO(100)/Ag(100), and to estimate their performance as spin qubits. Their analysis reveals that both atoms have a ground state that is suitable to perform efficient quantum coherent operations.

Dispersionless orbital excitations in (Li,Fe)OHFeSe superconductors

The superconducting critical temperature Tc of intercalated iron-selenide superconductor (Li,Fe)OHFeSe (FeSe11111) can be increased to 42 from 8 K of bulk FeSe. It shows remarkably similar electronic properties as the high-Tc monolayer FeSe and provides a bulk counterpart to investigate the origin of enhanced superconductivity. Unraveling the nature of excitations is crucial for understanding the pairing mechanism in high-Tc iron selenides. Here we use resonant inelastic x-ray scattering (RIXS) to investigate the excitations in FeSe11111. Our high-quality data exhibit several Raman-like excitations, which are dispersionless and isotropic in momentum transfer in both superconducting 28 K and 42 K samples. Using atomic multiplet calculations, we assign the low-energy ~0.3 and 0.7 eV Raman peaks as local eg − eg and eg − t2g orbital excitations. The intensity of these two features decreases with increasing temperature, suggesting a dominating contribution of the orbital fluctuations. Our results highlight the importance of the orbital degree of freedom for high-Tc iron selenides.

Orbital and spin character of doped carriers in infinite-layer nickelates

The discovery of superconductivity in infinite-layer nickelate thin films has produced fervent theoretical research about the doping evolution of their electronic structure. Here, by means of x-ray spectroscopy and atomic multiplet calculations, the authors show that doped holes are mainly introduced in Ni sites in a spin-singlet configuration. The dominant role of the Ni 3${d}_{{x}^{2}\ensuremath{-}{y}^{2}}$ band implies that infinite-layer nickelates are likely a strongly correlated electronic system, reminiscent of their cuprate siblings.

Hard x-ray photoemission spectroscopy of GdNi and HoNi

We study the electronic structure of GdNi and HoNi, which are magnetic materials with a Curie temperature ${T}_{c}=69$ and ${T}_{c}=36\phantom{\rule{0.28em}{0ex}}\mathrm{K}$, respectively. These materials are useful for magnetic refrigerator applications at low temperature as they exhibit a large magnetocaloric effect near ${T}_{c}$. We have used hard x-ray photoemission spectroscopy (HAXPES) to investigate the core-level and valence-band electronic states of GdNi and HoNi. HAXPES measurements of the Gd and Ho $3d, 4d, 4p, 5p$, and $4s$ core-level spectra have been compared with atomic multiplet calculations of ${\mathrm{Gd}}^{3+}$ and ${\mathrm{Ho}}^{3+}$ ionic configurations. The good match between the experimental and calculated spectra clarify the important role of spin-orbit coupling, as well as Coulomb and exchange interactions in the intermediate-coupling scheme. The core-level spectra also show plasmons in addition to the atomic multiplets. The Gd and Ho $4s$ spectra show clear evidence of exchange splitting. The Ni $2p$ and $3s$ spectra of GdNi and HoNi show a correlation satellite at a binding energy of 7 eV above their main peaks. The Ni $2p$ and Ni $3s$ spectra could be reproduced using charge transfer multiplet calculations. Valence-band HAXPES of GdNi and HoNi shows that the Gd $4f$ and Ho $4f$ features are also consistent with atomic multiplets and occur at high binding energies away from the Fermi level. The Ni $3d$ density of states are spread from the Fermi level to about 3 eV binding energy. The results indicate a partially filled Ni $3d$ band and show that the charge transfer model is not valid for describing the electronic structure of GdNi and HoNi.

Longitudinal and transverse electron paramagnetic resonance in a scanning tunneling microscope.

Electron paramagnetic resonance (EPR) spectroscopy is widely used to characterize paramagnetic complexes. Recently, EPR combined with scanning tunneling microscopy (STM) achieved single-spin sensitivity with sub-angstrom spatial resolution. The excitation mechanism of EPR in STM, however, is broadly debated, raising concerns about widespread application of this technique. We present an extensive experimental study and modeling of EPR-STM of Fe and hydrogenated Ti atoms on a MgO surface. Our results support a piezoelectric coupling mechanism, in which the EPR species oscillate adiabatically in the inhomogeneous magnetic field of the STM tip. An analysis based on Bloch equations combined with atomic-multiplet calculations identifies different EPR driving forces. Specifically, transverse magnetic field gradients drive the spin-1/2 hydrogenated Ti, whereas longitudinal magnetic field gradients drive the spin-2 Fe. Also, our results highlight the potential of piezoelectric coupling to induce electric dipole moments, thereby broadening the scope of EPR-STM to nonpolar species and nonlinear excitation schemes.

Probing defects and electronic structure of Eu doped t-Mg2B2O5 nanocrystals using X-ray absorption near edge spectroscopy and luminescence techniques

We report here the defects and electronic structure study of Eu (1%,3%,5%) doped t-Mg2B2O5 nanocrystals synthesized using low temperature combustion method, and probed using x-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray absorption near edge spectra (XANES), photoluminescence (PL) and thermoluminescence (TL). The XRD analysis of all samples shows single phase triclinic crystal structure and average crystallite size decreases with Eu doping in Mg2B2O5. The experimental XANES spectra of each sample acquired at Eu M5,4-edges were compared with simulated absorption edges using atomic-multiplet calculations, which clearly shows the presence of Eu3+ in Mg2B2O5. The O K-edge spectra of Eu doped Mg2B2O5 predicts the formation of O and Mg defects upon increasing Eu concentrations. The photoluminescence of Mg2-xEuxB2O5 nanocrystals at an excitation of 325 nm comprises of a group of sharp peaks owing to intra-4f transitions in Eu3+ and confirms the lowering of local symmetry with Eu concentration in Mg2B2O5. The effect of Eu doping on the trapping states was probed using TL after irradiating Mg2B2O5 with ultra-violet radiations (365 nm), which shows the presence of shallow and deep level trapping states. The corresponding activation energies of trapping states were determined using glow curve deconvolution method based on Kitti's general order equation.

Sensing alterations of the local environment of 3d, 4d, and 4f central ions in polyoxopalladates with soft X-ray magnetic dichroisms

Polyoxopalladates hosting 3d, 4d or 4f central ions form a new class of molecular materials with well-defined, tunable morphology and ions coordination to be considered as model systems for basic research. We investigated the isotropic X-ray absorption near-edge structure (XANES), X-ray magnetic circular dichroism (XMCD), and X-ray magnetic linear dichroism (XMLD) to monitor the influence of symmetry changes on electronic and magnetic properties. After a brief introductory review about recent results on 3d and 4d transition metal ions, we (i) show that a change of the coordination symmetry from cubic eightfold (tetrahedral) to sixfold (octahedral) reduces the magnetic moment of Co2+ significantly and (ii) investigate whether axial distortions can modify the 4f states of trivalent lanthanide ions. While for Gd3+ there is no effect visible within experimental uncertainties, changes were observed for Dy3+ and Ho3+. The results are compared to atomic multiplet calculations including the intra-atomic spin-dipole term 〈Tz〉. Furthermore, several experimental pitfalls are discussed that may lead to misinterpretation of X-ray absorption data but can be excluded in the present study.

Electronic structure investigation of GdNi using x-ray absorption, magnetic circular dichroism, and hard x-ray photoemission spectroscopy

GdNi is a ferrimagnetic material with a Curie temperature Tc = 69 K which exhibits a large magnetocaloric effect, making it useful for magnetic refrigerator applications. We investigate the electronic structure of GdNi by carrying out x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) at T = 25 K in the ferrimagnetic phase. We analyze the Gd M$_{4,5}$-edge ($3d$ - $4f$) and Ni L$_{2,3}$-edge ($2p$ - $3d$) spectra using atomic multiplet and cluster model calculations, respectively. The atomic multiplet calculation for Gd M$_{4,5}$-edge XAS indicates that Gd is trivalent in GdNi, consistent with localized $4f$ states. On the other hand, a model cluster calculation for Ni L$_{2,3}$-edge XAS shows that Ni is effectively divalent in GdNi and strongly hybridized with nearest neighbour Gd states, resulting in a $d$-electron count of 8.57. The Gd M$_{4,5}$-edge XMCD spectrum is consistent with a ground state configuration of S = 7/2 and L=0. The Ni L$_{2,3}$-edge XMCD results indicate that the antiferromagnetically aligned Ni moments exhibit a small but finite magnetic moment ( $m_{tot}$ $\sim$ 0.12 $\mu_B$ ) with the ratio $m_{o}/m_{s}$ $\sim$ 0.11. Valence band hard x-ray photoemission spectroscopy shows Ni $3d$ features at the Fermi level, confirming a partially filled $3d$ band, while the Gd $4f$ states are at high binding energies away from the Fermi level. The results indicate that the Ni $3d$ band is not fully occupied and contradicts the charge-transfer model for rare-earth based alloys. The obtained electronic parameters indicate that GdNi is a strongly correlated charge transfer metal with the Ni on-site Coulomb energy being much larger than the effective charge-transfer energy between the Ni $3d$ and Gd $4f$ states.

Nature of the magnetism of iridium in the double perovskite Sr2CoIrO6

We report on our investigation on the magnetism of the iridate double perovskite Sr$_2$CoIrO$_6$, a nominally Ir$^{5+}$ Van Vleck $J_{eff}=0$ system. Using x-ray absorption (XAS) and x-ray magnetic circular dichroism (XMCD) spectroscopy at the Ir-$L_{2,3}$ edges, we found a nearly zero orbital contribution to the magnetic moment and thus an apparent breakdown of the $J_{eff}=0$ ground state. By carrying out also XAS and XMCD experiments at the Co-$L_{2,3}$ edges and by performing detailed full atomic multiplet calculations to simulate all spectra, we discovered that the compound consists of about 90% Ir$^{5+}$ ($J_{eff}=0$) and Co$^{3+}$ ($S=2$) and 10% Ir$^{6+}$ ($S=3/2$) and Co$^{2+}$ ($S=3/2$). The magnetic signal of this minority Ir$^{6+}$ component is almost equally strong as that of the main Ir$^{5+}$ component. We infer that there is a competition between the Ir$^{5+}$-Co$^{3+}$ and the Ir$^{6+}$-Co$^{2+}$ configurations in this stoichiometric compound.

Magnetic and electronic properties at theγ−Al2O3/SrTiO3interface

The magnetic and electronic nature of the $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{Al}}_{2}{\mathrm{O}}_{3}/{\mathrm{SrTiO}}_{3}$ spinel/perovskite interface is explored by means of x-ray absorption spectroscopy. Polarized x-ray techniques combined with atomic multiplet calculations reveal localized magnetic moments assigned to ${\mathrm{Ti}}^{3+}$ at the interface with equivalent size for in- and out-of-plane magnetic field directions. Although magnetic fingerprints are revealed, the ${\mathrm{Ti}}^{3+}$ magnetism can be explained by a paramagnetic response at low temperature under applied magnetic fields. Modeling the x-ray linear dichroism results in a ${\mathrm{\ensuremath{\Delta}}}_{0}\ensuremath{\sim}1.9$ eV splitting between the ${t}_{2g}$ and ${e}_{g}$ states for the ${\mathrm{Ti}}^{4+}\phantom{\rule{4pt}{0ex}}3{d}^{0}$ orbitals. In addition these results indicate that the lowest energy states have the out-of-plane ${d}_{xz}/{d}_{yz}$ symmetry. The isotropic magnetic moment behavior and the lowest energy ${d}_{xz}/{d}_{yz}$ states are in contrast to the observations for the two-dimensional electron gas at the perovskite/perovskite interface of ${\mathrm{LaAlO}}_{3}/{\mathrm{SrTiO}}_{3}$ that exhibits an anisotropic magnetic ${d}_{xy}$ ground state.

Electronic properties of ultra-thin YCrO3 films

We report on the heteroepitaxial stabilization of YCrO3 ultra-thin films on LSAT (001) substrate. Using a combination of resonant X-ray absorption spectroscopy (XAS) and atomic multiplet cluster calculation, the electronic structure of YCrO3 thin film was investigated. Polarization dependent Cr L3,2 edge XAS measurements reveal the presence of x-ray linear dichroism spectrum uncharacteristic of a 3d3 electronic system in an octahedral crystal field. Atomic multiplet calculation demonstrates the critical importance of charge transfer energy, coulomb correlation strength, and hopping interaction in realizing this dichroism spectrum.

Enhanced photoluminescence response of Ca2+/Ba2+ substituted solid solutions of SrS:Ce phosphors

The quest of improving luminescence efficiency in alkaline earth sulfide phosphors has been of great interest due to their applications in diverse areas. We synthesized SrS:Ce0.05, Sr0.75Ba0.20S:Ce0.05, Sr0.75Ca0.20S:Ce0.05 and Sr0.75Ca0.10Ba0.10S:Ce0.05 phosphors using solid state diffusion method. X-ray diffraction patterns of all the samples were found similar to the cubic SrS phase except minor shifts in angles. To ascertain the valence state of Ce, near edge X-ray absorption fine structure spectroscopy was employed using synchrotron radiations. We simulated Ce M5,4-edges of Ce3+ ions using atomic multiplet calculations, which agrees well with the experimental data, clearly suggesting that Ce enters as Ce3+ in all the samples. The photoluminescence spectra of synthesized phosphors exhibit blue-green emission assigned to the 5d-4f transitions in Ce3+ levels, with minor shifts in wavelength. Interestingly, Ca2+/Ba2+substitution in SrS:Ce phosphors increases the PL intensity considerably. In comparison to SrS:Ce0.05 , PL intensity of Sr0.75Ca0.10Ba0.10S:Ce0.05 phosphors was enhanced by 2.7 times, which may be exploited in many optical applications.

Effects of rapid thermal annealing on the local environment, electronic structure and magnetic properties of Mn doped TiO2 thin films

In this report, nanostructure thin films of Ti0.97 Mn0.03 O2−δ were deposited on Si (001) substrate by pulsed laser deposition (PLD) technique, followed by rapid thermal annealing (RTA) in different ambient gases; O2, N2 and Ar. The RTA treatment dramatically affected the surface defects, local environment, electronic structure and magnetic properties of the films, where, annealing of the film in O2 gas recovered the dislocated atoms of oxygen vacancy (Vo) at the surfaces and induced a diamagnetic phase, whereas the annealing of film in N2 gas introduced Vo, reduced the valence state of Ti4+ (TiO2) into Ti3+ (Ti2O3) and induced ferromagnetic (FM) signal. Therefore, the change in the local atomic defects of Vo at the surface texture is likely to be responsible for the magnetic response. The presence of oxygen vacancy has been traced by means of Raman scattering and near edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements. The NEXAFS spectra were carried out in synchrotron facility at Ti/Mn L3,2 and O-K edges. The spectral feature at Ti L3,2 edges revealed the rutile phase of TiO2. The asymmetry of t2g and eg bands at the O-K edge confirmed the formation of Vo and reflected the modification in the O co-ordination around Ti4+cations. The Mn L3,2 edges revealed the incorporation of Mn ions in the TiO2 network with Mn2+ and Mn3+ mixed valence states. This different valance states (Mn2+ and Mn3+) is the basis for the ferromagnetism induced by Stoner spin-splitting of the local density of defects state at Fermi level (EF). The change in the magnetic moment of the films after RTA process is related to the change in the local density of defects band. Crystal field and charge transfer parameters were extracted roughly by using atomic multiplet calculations (theory).

Tuning the surface morphology and local atomic structure of Mn–TiO2 thin films using rapid thermal annealing

In this study, Ti0.95Mn0.05O2−δ nanostructured thin films were fabricated by pulsed laser deposition technique followed by rapid thermal annealing (RTA) in pure O2 and N2 atmospheres. The RTA process induced a substantial change in the surfaces morphology and local atomic structure around Ti4+ cation that have been studied by means of atomic force microscopy, Raman scattering and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Raman spectra of the films were resembled to that of TiO2 rutile phase, and the change in the width of Eg (434 cm−1) Raman active modes has been attributed to oxygen non-stoichiometry. NEXAFS spectra were carried out in synchrotron facility at Ti/Mn L3,2 edges and O-K edge. The ligand-field splitting, estimated from the energy difference between t2g and eg features in O K-edge spectra were ~ 2.81 eV for pristine and annealed film, which is a characteristic of the TiO2 rutile structure, and the asymmetry of t2g and eg bands at the O-K edge has been ascribed to oxygen vacancy (Vo2+). The annealing of film in O2 gas optimized the surface structure and healed the Vo2+ bridging, while the RTA in N2 gas introduced Vo and reduced the valence state of Ti4+ (TiO2) into Ti3+ (Ti2O3) that have been probed by comparing the NEXAFS spectra of N2 annealed film with the reference spectra of Ti2O3. Experimental and atomic multiplet calculations revealed that the Mn ions exist in 2+ valence state.

The key energy scales of Gd-based metallofullerene determined by resonant inelastic x-ray scattering spectroscopy

Endohedral metallofullerenes, formed by encaging Gd inside fullerenes like C80, can exhibit enhanced proton relaxitivities compared with other Gd-chelates, making them the promising contrast agents for magnetic resonance imaging (MRI). However, the underlying key energy scales of GdxSc3−xN@C80 (x = 1–3) remain unclear. Here, we carry out resonant inelastic x-ray scattering (RIXS) experiments on GdxSc3−xN@C80 at Gd N4,5-edges to directly study the electronic structure and spin flip excitations of Gd 4f electrons. Compared with reference Gd2O3 and contrast agent Gadodiamide, the features in the RIXS spectra of all metallofullerenes exhibit broader spectral lineshape and noticeable energy shift. Using atomic multiplet calculations, we have estimated the key energy scales such as the inter-site spin exchange field, intra-atomic 4f–4f Coulomb interactions, and spin-orbit coupling. The implications of these parameters to the 4f states of encapsulated Gd atoms are discussed.

Iron L2,3-Edge X-ray Absorption and X-ray Magnetic Circular Dichroism Studies of Molecular Iron Complexes with Relevance to the FeMoco and FeVco Active Sites of Nitrogenase.

Herein, a systematic study of a series of molecular iron model complexes has been carried out using Fe L2,3-edge X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopies. This series spans iron complexes of increasing complexity, starting from ferric and ferrous tetrachlorides ([FeCl4]−/2–), to ferric and ferrous tetrathiolates ([Fe(SR)4]−/2–), to diferric and mixed-valent iron–sulfur complexes [Fe2S2R4]2–/3–. This test set of compounds is used to evaluate the sensitivity of both Fe L2,3-edge XAS and XMCD spectroscopy to oxidation state and ligation changes. It is demonstrated that the energy shift and intensity of the L2,3-edge XAS spectra depends on both the oxidation state and covalency of the system; however, the quantitative information that can be extracted from these data is limited. On the other hand, analysis of the Fe XMCD shows distinct changes in the intensity at both L3 and L2 edges, depending on the oxidation state of the system. It is also demonstrated that the XMCD intensity is modulated by the covalency of the system. For mononuclear systems, the experimental data are correlated with atomic multiplet calculations in order to provide insights into the experimental observations. Finally, XMCD is applied to the tetranuclear heterometal–iron–sulfur clusters [MFe3S4]3+/2+ (M = Mo, V), which serve as structural analogues of the FeMoco and FeVco active sites of nitrogenase. It is demonstrated that the XMCD data can be utilized to obtain information on the oxidation state distribution in complex clusters that is not readily accessible for the Fe L2,3-edge XAS data alone. The advantages of XMCD relative to standard K-edge and L2,3-edge XAS are highlighted. This study provides an important foundation for future XMCD studies on complex (bio)inorganic systems.

Effect of Cu insertion on structural, local electronic/atomic structure and photocatalyst properties of TiO2, ZnO and Ni(OH)2 nanostructures: XANES-EXAFS study

We report detailed investigations on the synthesis, structural, morphology, electronic/atomic structure and photocatalyst properties of Cu doped TiO2, ZnO and Ni(OH)2 nanostructures. All of the samples were synthesized by using the chemical precipitation method. Samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS) and photocatalyst measurements. XRD studies revealed single phase nature of the samples and omitted the presence of trivial metallic or binary oxide phases. TiO2 set of samples have shown nanorod kind of morphology, however TEM images of ZnO and Ni(OH)2 set of samples depicted the spherical morphology of particles. XANES spectra at the Cu K-edge and Cu L-edge, along with the atomic multiplet calculations, revealed the predominance of Cu2+ ions in all of the samples, within the entire doping range. Ti L-edge and Ti K-edge XANES confirmed the existence of Ti4+ ions in the pure and Cu doped TiO2 samples with anatase local structure. Zn L-edge XANES results confirmed the divalent character of Zn ions in the pure and Cu doped ZnO, which is further validated by the Zn K-edge XANES. Ni L-edge and Ni K-edge XANES conveyed the +2 valence state of Ni ions in the pure and Cu doped Ni (OH)2 samples. EXAFS analysis at the Cu K-edge nullifies the formation of Cu metallic clusters and other trivial phases, suggesting random distribution of Cu atoms in the oxide materials. Though, local atomic arrangement of Cu ions is disparate in the different oxide compounds. As an application of the pure and Cu doped TiO2, ZnO and Ni(OH)2 nanostructures, towards the degradation of water pollutant dyes, we demonstrate that all of the samples can serve as effective photocatalyst materials towards the degradation of methyl orange aqueous pollutant dye under the UV-light irradiation.

Mechanistic insights on the electronic properties and electronic/atomic structure aspects in orthorhombic SrVO3 thin films: XANES-EXAFS study.

Correlations among the B-O6 octahedra distortions, existing polymorphous phases, band structures and electronic conductivities of ABO3 perovskites are matters for debate and require a deep understanding of their local atomic/electronic structures and diverse assets. In this study, to illustrate the distortion in V-O6 octahedra and its implication on the band structure and electronic properties, spectroscopic investigations on the RF-sputtering grown insulating SrVO3 thin films were employed using X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). V K-edge and V L3,2-edge XANES, along with atomic multiplet calculations, have confirmed the 4+ oxidation state of V ions in the pristine and annealed SrVO3 thin films. Lower t2g/eg peak intensity ratio and smaller energy separation between t2g and eg peaks in the O K-edge XANES spectra, compared to the VO2 reference sample, have confirmed a larger V-O6 distortion in the orthorhombic SrVO3 thin films. Moreover, from the EXAFS data analysis, the local orthorhombic structure has been identified in the pristine and annealed SrVO3 thin films, compelling significant distortion in the V-O6 octahedra. Dimerization in the vanadium chains and V-V twisting, caused by V-O6 octahedra distortion, manifests a miscellaneous ligand field interaction between O 2p and V 3d orbitals and facilitates (i) a larger separation between the bonding and antibonding d‖ orbitals and (ii) an upward shift of the π* band in the band structure, leading to larger band gaps in the insulating SrVO3 thin films. Our spectroscopy results may open up new avenues for the mechanism of insulating/conducting character in other complicated perovskite materials using XANES-EXAFS.