Skeletal Vibrational Modes Research Articles

Twisted intramolecular charge transfer of nitroaromatic push\u2013pull chromophores

The structural changes during the intramolecular charge transfer (ICT) of nitroaromatic chromophores, 4-dimethylamino-4′-nitrobiphenyl (DNBP) and 4-dimethylamino-4′-nitrostilbene (DNS) were investigated by femtosecond stimulated Raman spectroscopy (FSRS) with both high spectral and temporal resolutions. The kinetically resolved Raman spectra of DNBP and DNS in the locally-excited and charge-transferred states of the S1 state appear distinct, especially in the skeletal vibrational modes of biphenyl and stilbene including ν8a and νC=C. The ν8a of two phenyls and the νC=C of the central ethylene group (only for stilbene), which are strongly coupled in the planar geometries, are broken with the twist of nitrophenyl group with the ICT. Time-resolved vibrational spectroscopy measurements and the time-dependent density functional theory simulations support the ultrafast ICT dynamics of 220–480 fs with the twist of nitrophenyl group occurring in the S1 state of the nitroaromatic chromophores. While the ICT of DNBP occurs via a barrier-less pathway, the ICT coordinates of DNS are strongly coupled to several low-frequency out-of-phase deformation modes relevant to the twist of the nitrophenyl group.

Funneling dynamics in a phenylacetylene trimer: Coherent excitation of donor excitonic states and their superposition.

Funneling dynamics in conjugated dendrimers has raised great interest in the context of artificial light-harvesting processes. Photoinduced relaxation has been explored by time-resolved spectroscopy and simulations, mainly by semiclassical approaches or referring to open quantum systems methods, within the Redfield approximation. Here, we take the benefit of an ab initio investigation of a phenylacetylene trimer, and in the spirit of a divide-and-conquer approach, we focus on the early dynamics of the hierarchy of interactions. We build a simplified but realistic model by retaining only bright electronic states and selecting the vibrational domain expected to play the dominant role for timescales shorter than 500fs. We specifically analyze the role of the in-plane high-frequency skeletal vibrational modes involving the triple bonds. Open quantum system non-adiabatic dynamics involving conical intersections is conducted by separating the electronic subsystem from the high-frequency tuning and coupling vibrational baths. This partition is implemented within a robust non-perturbative and non-Markovian method, here the hierarchical equations of motion. We will more precisely analyze the coherent preparation of donor states or of their superposition by short laser pulses with different polarizations. In particular, we extend the π-pulse strategy for the creation of a superposition to a V-type system. We study the relaxation induced by the high-frequency vibrational collective modes and the transitory dissymmetry, which results from the creation of a superposition of electronic donor states.

Infrared Spectroscopy in the Middle Frequency Range for Various Imidazolium Ionic Liquids-Common Spectroscopic Characteristics of Vibrational Modes with In-Plane +C(2)-H and +C(4,5)-H Bending Motions and Peak Splitting Behavior Due to Local Symmetry Breaking of Vibrational Modes of the Tetrafluoroborate Anion.

Various alkyl-methylimidazolium ionic liquids (ILs) were inspected using infrared spectroscopy in the middle frequency range. In the 1050–1200 cm–1 range, there is a skeletal vibrational mode accompanied with a large in-plane +C(2)–H bending motion and +C(4)–H and +C(5)–H motions, and in the 1500–1650 cm–1 range, there are two skeletal vibrational modes with in-plane +C(4,5)–H bending motions. Interestingly, in both ranges, we found that skeletal vibrational modes with a large in-plane +C(2)–H bending motion and in-plane +C(4,5)–H bending motions are insensitive to increases in the basicity of anions or the strengthening of hydrogen bond-type interactions, and the behaviors are completely different from those in the +C–H stretching vibrational modes in the 3000–3200 cm–1 range and the skeletal vibrational modes with large out-of-plane +C–H motions in the 700–950 cm–1 range. Furthermore, in alkyl-methylimidazolium tetrafluoroborate [Cnmim+][BF4–] ILs, we found that absorption due to the (threefold) degenerate vibrational mode of [BF4–] was observed as a broad absorption band with three splitting peaks in the 900–1150 cm–1 range as a result of local symmetry breaking due to the cation–anion interactions.

Ultrafast intramolecular proton transfer reactions and solvation dynamics of DMSO.

Ultrafast intramolecular proton transfers of 1,2-dihydroxyanthraquinone (alizarin-h2) and its deuterated product (alizarin-d2) in dimethyl sulfoxide (DMSO) have been investigated by femtosecond stimulated Raman spectroscopy. The population dynamics in the solute vibrational mode of νC=O and the coherent oscillations observed in all of the skeletal vibrational modes νC=O and νC=C clearly showed the ultrafast excited-state intramolecular proton transfer dynamics of 110 and 170 fs for alizarin-h2 and alizarin-d2, respectively. Interestingly, we have observed that the solvent vibrational modes νS=O and νCSC may also represent ultrafast structural dynamics at the frequencies for its “free” or “aggregated” species. From the kinetic analysis of the νS=O and νCSC modes of DMSO, the ultrafast changes in the solvation or intermolecular interactions between DMSO molecules initiated by the structural changes of solute molecules have been thoroughly investigated. We propose that the solvent vibrational modes νS=O and νCSC of DMSO can be used as a “sensor” for ultrafast chemical reactions accompanying the structural changes and subsequent solute-solvent interactions.

Ultrafast Intramolecular Proton Transfer of Alizarin Investigated by Femtosecond Stimulated Raman Spectroscopy.

We report time-resolved stimulated Raman spectra of alizarin in DMSO solution with 403 nm excitation. Upon photoexcitation, the intramolecular proton transfer reaction of alizarin occurs in 70-80 fs, which is confirmed by both the population growth and the frequency and bandwidth changes of skeletal vibrational modes of alizarin. Interestingly, the vibrational frequencies of ν(C═C) and ν(C═O) show opposite shifts during the reaction, which may implicate changes in the resonance structure of anthraquinone and the attached carbonyl group. Vibrational relaxation in the potential surface of the proton transferred tautomer of alizarin and the population decay occurring with two distinct time scales were also observed in addition to the solvation dynamics of DMSO solvent molecules.

Intermode Coupling Drives the Irreversible Tautomerization in Porphycene on Copper(111) Induced by Scanning Tunnelling Microscopy.

In this contribution, we develop a nonadiabatic theory that explains, from first-principles, the recently reported irreversible trans → cis tautomerization of porphycene on Cu(111) induced by a scanning tunnelling microscope at finite bias. The inelastic contribution to the STM current is found to excite a large number of skeletal vibrational modes of the molecule, thereby inducing a deformation of the potential energy landscape along the hydrogen transfer coordinate. Above a threshold bias, the stability of the tautomers is reversed, which indirectly drives the reaction via intermode coupling. The proposed potential deformation term accounts effectively for the excitation of all internal vibrational modes without increasing the dimensionality of the problem. The model yields information about reaction rates, explains the reaction irreversibility at low temperatures, and accounts for the presence of resonant processes.

Understanding the Structural Evolution of Single Conjugated Polymer Chain Conformers.

Single molecule photoluminescence (PL) spectroscopy of conjugated polymers has shed new light on the complex structure–function relationships of these materials. Although extensive work has been carried out using polarization and excitation intensity modulated experiments to elucidate conformation-dependent photophysics, surprisingly little attention has been given to information contained in the PL spectral line shapes. We investigate single molecule PL spectra of the prototypical conjugated polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) which exists in at least two emissive conformers and can only be observed at dilute levels. Using a model based on the well-known “Missing Mode Effect” (MIME), we show that vibronic progression intervals for MEH-PPV conformers can be explained by relative contributions from particular skeletal vibrational modes. Here, observed progression intervals do not match any ground state Raman active vibrational frequency and instead represent a coalescence of multiple modes in the frequency domain. For example, the higher energy emitting “blue” MEH-PPV form exhibits PL maxima at ~18,200 cm−1 with characteristic MIME progression intervals of ~1200–1350 cm−1, whereas the lower energy emitting “red” form peaks at ~17,100 cm−1 with intervals in the range of ~1350–1450 cm−1. The main differences in blue and red MEH-PPV chromophores lie in the intra-chain order, or, planarity of monomers within a chromophore segment. We demonstrate that the Raman-active out-of-plane C–H wag of the MEH-PPV vinylene group (~966 cm−1) has the greatest influence in determining the observed vibronic progression MIME interval. Namely, larger displacements (intensities)—indicating lower intra-chain order—lower the effective MIME interval. This simple model provides useful insights into the conformational characteristics of the heterogeneous chromophore landscape without requiring costly and time-consuming low temperature or single molecule Raman capabilities.

Vibration Modes at Terahertz and Infrared Frequencies of Ionic Liquids Consisting of an Imidazolium Cation and a Halogen Anion.

The terahertz and infrared frequency vibration modes of room-temperature ionic liquids with imidazolium cations and halogen anions were extensively investigated. There is an intermolecular vibrational mode between the imidazolium ring of an imidazolium cation, a halogen atomic anion with a large absorption coefficient and a broad bandwidth in the low THz frequency region (13–130 cm−1), the intramolecular vibrational modes of the alkyl-chain part of an imidazolium cation with a relatively small absorption coefficient in the mid THz frequency region (130–500 cm−1), the intramolecular skeletal vibrational modes of an imidazolium ring affected by the interaction between the imidazolium ring, and a halogen anion with a relatively large absorption coefficient in a high THz frequency region (500–670 cm−1). Interesting spectroscopic features on the interaction between imidazolium cations and halogen anions was also obtained from spectroscopic studies at IR frequencies (550–3300 cm−1). As far as the frequency of the intermolecular vibrational mode is concerned, we found the significance of the reduced mass in determining the intermolecular vibration frequency.

DFT and ab initio quantum chemical studies on p-cyanobenzoic acid

The Fourier transform infrared (FTIR) and FT-Raman spectra of p-cyanobenzoic acid (CBA) have been recorded in the range 4000–400 and 4000–100 cm −1, respectively. The complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the observed FTIR and FT-Raman data. The vibrational frequencies determined experimentally were compared with theoretical wavenumbers obtained from ab initio HF and DFT-B3LYP gradient calculations employing 6-31G**, 6-311++G** and cc-pVTZ basis sets for the optimised geometry of the compound. The geometry and normal modes of vibration obtained from the HF and DFT methods are in good agreement with the experimental data. The normal coordinate analysis was also carried out with ab initio force fields utilising Wilson's FG matrix method. The interactions of cyano and carboxylic acid groups with the skeletal vibrational modes were investigated.

FAR-INFRARED SPECTROSCOPY OF CATIONIC POLYCYCLIC AROMATIC HYDROCARBONS: ZERO KINETIC ENERGY PHOTOELECTRON SPECTROSCOPY OF PENTACENE VAPORIZED FROM LASER DESORPTION

The distinctive set of infrared (IR) emission bands at 3.3, 6.2, 7.7, 8.6, and 11.3{\mu}m are ubiquitously seen in a wide variety of astrophysical environments. They are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. However, not a single PAH species has yet been identified in space, as the mid-IR vibrational bands are mostly representative of functional groups and thus do not allow one to fingerprint individual PAH molecules. In contrast, the far-IR (FIR) bands are sensitive to the skeletal characteristics of a molecule, hence they are important for chemical identification of unknown species. With an aim to offer laboratory astrophysical data for the Herschel Space Observatory, Stratospheric Observatory for Infrared Astronomy, and similar future space missions, in this work we report neutral and cation FIR spectroscopy of pentacene (C_22H_14), a five-ring PAH molecule. We report three IR active modes of cationic pentacene at 53.3, 84.8, and 266{\mu}m that may be detectable by space missions such as the SAFARI instrument on board SPICA. In the experiment, pentacene is vaporized from a laser desorption source and cooled by a supersonic argon beam. We have obtained results from two-color resonantly enhanced multiphoton ionization and two-color zero kinetic energy photoelectron (ZEKE) spectroscopy. Several skeletal vibrational modes of the first electronically excited state of the neutral species and those of the cation are assigned, with the aid of ab initio and density functional calculations.

FTIR, FT-Raman, ab initio and density functional studies on 4-methyl-1,3-dioxolan-2-one and 4,5-dichloro-1,3-dioxolan-2-one

The Fourier transform infrared (FTIR) and FT-Raman spectra of 4-methyl-1,3-dioxolan-2-one and 4,5-dichloro-1,3-dioxolan-2-one have been recorded in the range 3700–400 and 3700–100 cm −1, respectively. The complete vibrational assignment and analysis of the fundamental modes of the compounds were carried out using the observed FTIR and FT-Raman data. The vibrational frequencies determined experimentally were compared with those obtained theoretically from ab initio HF and DFT-B3LYP gradient calculations employing 6-311++G** and cc-pVTZ basis sets for the optimised geometries of the compounds. The geometries and normal modes of vibration obtained from the HF and DFT methods are in good agreement with the experimental data. The normal coordinate analysis was also carried out with ab initio force fields utilising Wilson's FG matrix method. The interactions of the skeletal vibrational modes were investigated.

Vibrational Coherence in Polar Solutions of ZnII tetrakis(N-methylpyridyl)porphyrin with Soret-Band Excitation: Rapidly Damped Intermolecular Modes with Clustered Solvent Molecules and Slowly Damped Intramolecular Modes from the Porphyrin Macrocycle

Ground-state coherent wavepacket motions arising from intermolecular modes with clustered, first-shell solvent molecules were observed using the femtosecond dynamic absorption technique in polar solutions of Zn(II) meso-tetrakis(N-methylpyridyl)porphyrin (ZnTMPyP) with excitation in the Soret absorption band. As was observed previously in bacteriochlorophyll a solution, the pump-probe transients in ZnTMPyP solutions are weakly modulated by slowly damped (effective damping time gamma > 1 ps) features that are assigned to intramolecular modes, the skeletal normal modes of vibration of the porphyrin. The 40 cm(-1) and 215 cm(-1) modes from the metal-doming and metal-solvent-ligand modes, respectively, are members of this set of modulation components. A slowly damped 2-4 cm(-1) component is assigned to the internal rotation of the N-methylpyridyl rings with respect to the porphyrin macrocycle; this mode obtains strong resonance Raman intensity enhancement from an extensive delocalization of pi-electron density from the porphyrin in the ground state onto the rings in the pi* excited states. The dominant features observed in the pump-probe transients are a pair of rapidly damped (gamma < 250 fs) modulation components arising from intermolecular modes with solvent molecules. This structural assignment is supported by an isotope-dependent shift of the average mode frequencies in methanol and perdeuterated methanol. The solvent dependence of the mean intermolecular mode frequency is consistent with a van der Waals intermolecular potential that has significant contributions only from the London dispersion and induction interactions; ion-dipole or ion-induced-dipole terms do not make large contributions because the pi-electron density is not extensively delocalized onto the N-methylpyridyl rings. The modulation depth associated with the intermolecular modes exhibits a marked dependence on the electronic structure of the solvent that is probably related to the degree of covalency; the strongest modulations are observed in acetonitrile and dimethylsulfoxide. The results strongly support a structural assignment of the low-frequency modes that are coupled to the primary and secondary electron-transfer reactions in photosynthetic reaction centers to intermolecular modes between the redox-active chromophores and first-solvation shell groups from the surrounding protein, and an important additional function of the intermolecular modes in the stabilization of charged intermediates is suggested.

Specific coupling between the 13-keto carbonyl and chlorin skeletal vibrational modes of synthetic 13 1- 18O-(un)labelled metallochlorophyll derivatives

Metal complexes of methyl 13 1- 18O-labelled pyropheophorbide- a 1-M– 18O (M = Zn, Cu and Ni) were prepared by metallation of the 18O-labelled free base ( 1- 18O) and 18O-labelling of unlabelled nickel complex ( 1-Ni). The FT-IR spectra of 1-Zn and 1-Zn– 18O in CH 2Cl 2 showed that the 13-keto carbonyl stretching vibration mode moved to about a 30-cm −1 lower wavenumber by 18O-labelling of the 13 1-oxo moiety. In 1-Cu– 18O and 1-Ni– 18O, the 13-C 18O stretching modes were close to the highest-energy wavenumber mode of chlorin skeletal C–C/C–N vibrations at around 1650 cm −1 and they were coupled in CH 2Cl 2 to give two split IR bands (Fermi resonance). A similar coupling was observed in the resonance Raman scattering of 1-Ni– 18O in the solid state. The hydrogen-bonded 13-C 16O vibration mode of 1-Ni similarly coupled with the skeletal C–C/C–N mode in CCl 4 containing 1% (v/v) 1,1,1,3,3,3-hexafluoro-2-propanol, while such a coupling was not observed in a neat CCl 4 solution of 1-Ni possessing the 13-C 16O free from any interaction. The skeletal C–C/C–N band selectively coupled with the 13-C O, not with the 3-C O, when the difference in their peak maxima was less than 20 cm −1.

Zero kinetic energy photoelectron spectroscopy of tetracene using laser desorption for vaporization

Far infrared (FIR) spectroscopy of polycyclic aromatic hydrocarbons is of particular interest to astrophysics since vibrational modes in this range are representative of the molecular size and shape. This information is hence important for identification of chemical compositions and for modeling of the IR spectrum observed in the outer space. In this work, we report neutral and cation FIR spectroscopy of tetracene vaporized from a laser desorption source. Results from two-color resonantly enhanced multiphoton ionization and two-color zero kinetic energy photoelectron spectroscopy will be presented. Several skeletal vibrational modes of the first electronically excited state of the neutral species and those of the cation are assigned, with the aid of ab initio and density functional calculations. The adiabatic ionization potential is determined to be 55 918 +/- 7 cm(-1). Interestingly, all observed vibrational modes can be rationalized based on a simple Huckle calculation, i.e., by observing the addition or elimination of nodal planes due to electronic excitation and/or ionization. Limited by the Franck-Condon principle and the rigidity of the molecular frame of tetracene, only IR forbidden modes are observed in this work.

阴离子作用下的小牛胸腺DNA的表面增强拉曼光谱研究

Dependence of surface-enhanced Raman scattering (SERS) from Calf thymus DNA on anions is investigated. With the silver colloid, the bands at 732, 960 and 1333 cm-1 for adenine (A), 1466 cm-1 for deoxyribose, and 1652 cm-1 for the C=O group of thymine (T) are observably enhanced. With the presence of the Cl- or SO^(2-)_(4) anions, the bands at 732 and 1326/1329 cm-1 for the symmetric stretching and skeletal vibrational modes of adenine (A) are dramatically enhanced, and the enhancement effect with the SO^(2-)_(4) ion is more than that with the Cl_ ion. The experimental results show that the DNA molecule can be adsorbed on the silver colloid particles through the C6N and N7 of adenine (A), the C=O of thymine (T) and deoxyribose. Moreover, the formed hydrogen bonding of the Cl_ or SO^(2-)_(4) ions to the C6NH2 group of adenine (A) can induce larger C6N electronegativity, which is favor for the C6N/N7 cooperative adsorption on the (Ag)^(+)_(n) colloid particles.

Probes of the Metal-to-Ligand Charge-Transfer Excited States in Ruthenium-Am(m)ine-Bipyridine Complexes: The Effects of NH/ND and CH/CD Isotopic Substitution on the 77 K Luminescence

The effects of ligand perdeuteration on the metal-to-ligand charge-transfer (MLCT) excited-state emission properties at 77 K are described for several [Ru(L)(4)bpy](2+) complexes in which the emission process is nominally [uIII,bpy-] --> [RuII,bpy]. The perdeuteration of the 2,2'-bipyridine (bpy) ligand is found to increase the zero-point energy differences between the ground states and MLCT excited states by amounts that vary from 0 +/- 10 to 70 +/- 10 cm(-1) depending on the ligands L. This indicates that there are some vibrational modes with smaller force constants in the excited states than in the ground states for most of these complexes. These blue shifts increase approximately as the energy difference between the excited and ground states decreases, but they are otherwise not strongly correlated with the number of bipyridine ligands in the complex. Careful comparisons of the [Ru(L)(4)(d(8)-bpy)](2+) and [Ru(L)(4)(h(8)-bpy](2+) emission spectra are used to resolve the very weak vibronic contributions of the C-H stretching modes as the composite contributions of the corresponding vibrational reorganizational energies. The largest of these, 25 +/- 10 cm(-1), is found for the complexes with L = py or bpy/2 and smaller when L = NH(3). Perdeuteration of the am(m)ine ligands (NH(3), en, or [14]aneN(4)) has no significant effect on the zero-point energy difference, and the contributions of the NH stretching vibrational modes to the emission band shape are too weak to resolve. Ligand perdeuteration does increase the excited-state lifetimes by a factor that is roughly proportional to the excited-state-ground-state energy difference, even though the CH and NH vibrational reorganizational energies are too small for nuclear tunneling involving these modes to dominate the relaxation process. It is proposed that metal-ligand skeletal vibrational modes and configurational mixing between metal-centered, bpy-ligand-centered, and MLCT excited states are important in determining the zero-point energy differences, while a large number of different combinations of relatively low-frequency vibrational modes must contribute to the nonradiative relaxation of the MLCT excited states.

Binding of Cd2+ to Self-Assembled Bilayers Bearing Pyridine Terminal Groups: Attenuated Total Reflection Fourier Transform Infrared Spectroscopic Studies

Various aspects of the adsorption of Cd2+ on self-assembled monolayers (SAMs) of 4-heptadecylpyridine (HDpy) and 7-tridecyl-4-methyl-1,10-bipyridine (TMbipy) supported on an octadecylsilane (ODS)-modified Ge prism have been examined both ex situ (dry) and in situ (in the presence of aqueous solutions) using attenuated total reflection Fourier transform infrared spectroscopy. In direct analogy with the behavior found for a variety of genuine pyridine (py) and bipyridine (bipy) metal ion complexes, Cd2+ binding to both SAMs led to shifts in the skeletal vibrational modes of the corresponding uncoordinated ligands in the region 1650-1400 cm(-1), toward higher energies. Analysis of spectra acquired ex situ for HDpy/ODS/Ge and TMbipy/ODS/Ge before and after exposure to 0.1 mM [Cd2+] yielded values for the fraction of uncoordinated py, theta(py(un)), and uncoordinated bipy, theta(bipy(un)), of about 0.5 and about 0.1, respectively. The features attributed to the py(un) groups for spectra collected for HDpy/ODS/Ge in situ and ex situ were found to be virtually identical, making it possible to isolate by graphical means the most prominent band of py(co) centered at about 1615 cm(-l) for HDpy/ODS/Ge collected in situ. The resulting bands for pure py(co) and pyun in situ were then used to deconvolute spectra recorded in situ for HPpy/ODS/Ge in contact with Cd2+containing solutions in the range 10 nM < [Cd2+] < 0.1 mM, from which information regarding the adsorption isotherm was obtained.

Electronic and Vibrational Properties of Porphycene Anions

Resonance Raman spectra of the anion radical and dianion of a free-base porphycene are obtained, and quantum chemical calculations based on density functional theory methods are carried out in order to derive the force fields of porphycene anions. Normal modes with similar vibrational characteristics are correlated by examining the overlaps between the different redox states in order to characterize the frequency shifts measured for reduced porphycenes in certain skeletal vibrational modes. The observed resonance Raman behavior is generally consistent with the formation of the π anion radical and π dianion of trans-porphycene with C 2 h symmetry upon reduction.

Resonance Raman characterization of porphycene anions

Resonance Raman spectra of reduced porphycenes were measured in an effort to characterize structural changes concomitant with chemical reduction. Frequency shifts were observed for reduced porphycenes in certain skeletal vibrational modes. The observed resonance Raman behavior was generally consistent with the results of vibrational analysis by quantum chemical calculations based on density functional methods.

Raman and FTIR spectroscopies of fluorescein in solutions

Raman and Fourier transform-infra red (FT-IR) spectroscopies of fluorescein in aqueous solutions have been investigated in the pH range from 9.1 to 5.4. At pH 9.1 fluorescein is in the dianion form. At pH 5.4, fluorescein is a mixture of monoanion (∼85%), dianion and neutral forms (together ∼15%). The fluorescence quantum yield drops from 0.93 for the dianion form to 0.37 for the monoanion form. The Raman and FT-IR studies focused on the frequency range from 1000 to 1800 cm −1 which contains the skeletal vibrational modes of the xanthene moiety of fluorescein. At pH 9.1, the spectroscopic feature of fluorescein dianion are consistent with a picture of an electron delocalized among the xanthene moiety and two identical oxygens attached to opposite ends of the xanthene moiety, forming a very symmetric structure. The characteristic of fluorescein dianion is the presence of the phenoxide-like stretch at 1310 cm −1. At pH 5.4, fluorescein monoanion has lost the symmetric structure characteristic of the dianion. The spectra of the monoanion have distinctive contributions from the phenolic bend at 1184 cm −1. The assignments of the vibrational bands shown in Raman and FT-IR spectra are given based on both literature and the ab initio calculations at the Hartree–Fock level with HF/6-31++G* basis set. Excellent correlation is found between the experimental and calculated spectra.