Resonance Raman Spectra Research Articles

Continuously wavelength tunable, continuous wave laser ideal for UV Raman spectroscopy

AbstractWe utilize a novel, high‐power, tunable, continuous wave (CW) deep UV laser to measure resonance Raman spectra of phenolate solutions with high signal‐to‐noise ratios (SNR). In UV resonance Raman (UVRR), increased coupling of the excitation light with a chromophore can transfer molecules into excited states that cause increased heating and photochemistry. Deep UV lasers have traditionally utilized high peak powers to enable efficient single‐pass nonlinear conversion from visible into near infrared light. Nonlinear phenomena such as the formation of transient radical species, Raman saturation, thermal heating, and dielectric breakdown can introduce extraneous light sources that can complicate the interpretation of the Raman spectrum. Dielectric breakdown can increase the baseline, increase noise, and sometimes saturate the detector, preventing Raman detection. Spontaneous Raman scattering intensities should scale linearly with the excitation light intensity. However, this linear behavior does not always occur with pulsed laser excitation. This occurs because stimulated Raman scattering can cause a superlinear intensity response, or transient absorption can cause sublinear intensity responses. CW laser excitation excites samples with electric fields that are much lower than typical pulsed laser excitation. This eliminates the nonlinear responses. The geometry of our new CW laser enables high gain in the harmonic generation cavities that achieve high harmonic generation efficiencies. Average power in the deep UV is >30 mW for wavelengths as short as 206 nm. In the work here, we demonstrate that CW excitation is ideal for resonance Raman measurements in general to reduce spectral complexity.

Spectral Analysis on Cuba-Lumacaftor: Cubane as Benzene Bioisosteres of Lumacaftor.

In this paper, we theoretically investigate the electronic structure and physical properties of cuba-lumacaftor, cubane as benzene bioisosteres of lumacaftor, stimulated by recent experimental reports [Wiesenfeldt M. P.; Nature2023, 618, 513-518]. The permanent electric dipole moments of cuba-lumacaftor in neutral, acidic, and alkaline environments are significantly enlarged than that of lumacaftor, significantly promoting the interaction between cuba-lumacaftor and surrounding polar solvent environments and resulting in pH-independent high solubility and pharmacological activity. Furthermore, electronic circular dichroism (ECD) spectra reveal that the chirality of cuba-lumacaftor is much decreased compared to that of lumacaftor. Raman spectra and resonance Raman spectra combined with polarizability also reveal the vibrational information on cuba-lumacaftor. Our results promote a deeper understanding of better pharmacological activity.

Spectral Physics of Stable Cu(III) Produced by Oxidative Addition of an Alkyl Halide.

In this paper, we theoretically investigated spectral physics on Cu(III) complexes formed by the oxidative addition of α-haloacetonitrile to ionic and neutral Cu(I) complexes, stimulated by recent experimental reports. Firstly, the electronic structures of reactants of α-haloacetonitrile and neutral Cu(I) and two kinds of products of Cu(III) complexes are visualized with the density of state (DOS) and orbital energy levels of HOMO and LUMO. The visually manifested static and dynamic polarizability as well as the first hyperpolarizability are employed to reveal the vibrational modes of the normal and resonance Raman spectra of two Cu(III) complexes. The nuclear magnetic resonance (NMR) spectra are not only used to identify the reactants and products but also to distinguish between two Cu(III) complexes. The charge difference density (CDD) reveals intramolecular charge transfer in electronic transitions in optical absorption spectra. The CDDs in fluorescence visually reveal electron-hole recombination. Our results promote a deeper understanding of the physical mechanism of stable Cu(III) produced by the oxidative addition of an alkyl halide.

QERaman: An open-source program for calculating resonance Raman spectra based on Quantum ESPRESSO

We present an open-source program QERaman that computes first-order resonance Raman spectroscopy of materials using the output data from Quantum ESPRESSO. Complex values of Raman tensors are calculated based on the quantum description of the Raman scattering from calculations of electron-photon and electron-phonon matrix elements, which are obtained by using the modified Quantum ESPRESSO. Our program also calculates the resonant Raman spectra as a function of incident laser energy for linearly- or circularly-polarized light. Hands-on tutorials for graphene and MoS2 are given to show how to run QERaman. All codes, examples, and scripts are available on the GitHub repository. Program summaryProgram Title:QERamanCPC Library link to program files:https://doi.org/10.17632/ddcrrrmxw9.1Developer's repository link:https://github.com/nguyen-group/QERamanLicensing provisions: GNU General Public Licence 3.0Programming language: FortranExternal routines:Quantum ESPRESSO v7.2Nature of problem: Resonance Raman spectra with first-principles calculations.Solution method: The Raman intensity formula is given by the quantum theory, in which the electron-photon and the electron-phonon matrix elements are obtained from the modified Quantum ESPRESSO package.

Probing the Fucoxanthin-Chlorophyll a/c-Binding Proteins (FCPs) of the Marine Diatom Fragilariopsis sp. by Resonance Raman Spectroscopy.

We report resonance Raman spectra of the light-harvesting fucoxanthin-chlorophyll a/c-binding proteins (FCPs) of marine diatom Fragilariopsis sp. The Raman shifts in the 15N-isotope-enriched diatom provide the first spectroscopic evidence for the characterization of the Ca-N marker bands and, thus, of the penta- and hexacoordinated states of chlorophylls a/c in the FCPs. Under 405 and 442 nm Raman excitations, all of the marker bands of Chl a/c are observed and the isotope-based assignments provide new information concerning the structure of Chls a/c in the FCPs and their interactions with the protein environment. Therefore, the Raman spectrum at 405 nm originates from the π-π* transitions of Chl a/c and not from a different, non π-π* electronic transition, as previously reported (BBA Bioenergetics, 2010, 1797, 1647-1656). Based on the 15N isotope shifts of the Ca-N and in conjunction with other marker bands, two distinct conformations of five- and six-coordinated Chl a and Chl c are observed. In addition, two keto carbonyls were observed at 1679 (strong H-bonded) and 1691 cm-1 (weak H-bonded) in both the 405 and 442 nm Raman spectra, respectively. Collectively, the results provide solid evidence of the nature of the vibrational modes of the active Chl a/c photosynthetic pigments in the FCPs.

Experimental Assessment of the Electronic and Geometrical Structure of a Near-Infrared Absorbing and Highly Fluorescent Microbial Rhodopsin.

The recently discovered Neorhodopsin (NeoR) exhibits absorption and emission maxima in the near-infrared spectral region, which together with the high fluorescence quantum yield makes it an attractive retinal protein for optogenetic applications. The unique optical properties can be rationalized by a theoretical model that predicts a high charge transfer character in the electronic ground state (S0) which is otherwise typical of the excited state S1 in canonical retinal proteins. The present study sets out to assess the electronic structure of the NeoR chromophore by resonance Raman (RR) spectroscopy since frequencies and relative intensities of RR bands are controlled by the ground and excited state's properties. The RR spectra of NeoR differ dramatically from those of canonical rhodopsins but can be reliably reproduced by the calculations carried out within two different structural models. The remarkable agreement between the experimental and calculated spectra confirms the consistency and robustness of the theoretical approach.

Synchrotron-based UV resonance Raman spectroscopy probes size confinement, termination effects, and anharmonicity of carbon atomic wires

Vibrational and electronic properties and anharmonicity of sp-carbon atomic wires (i.e., polyynes) have been studied using resonance Raman spectroscopy, focusing on the confinement effects connected to their structure (length and termination). We exploited the fine tunability of the synchrotron radiation to resonantly excite short H-, CH3-, and CN-capped carbon atomic wires at their vibronic transitions in the deep UV. We report for the first time the resonance Raman spectra of size-selected CH3-capped polyynic wires (HCnCH3, n = 8–12) and CN-capped wires (HC6CN and HC12CN). We observed that the degree of π-electron conjugation increases with the wire length and is related to the specific termination. The analysis of multiple quanta Raman overtone bands shows that the anharmonic correction of the vibrational potential energy becomes increasingly relevant as the wire length increases. Finally, studying the vibronic lines of the UV absorption spectra allows the determination of an effective displacement parameter between the minima of the ground and the low-lying excited state, proving that the strong electron-phonon coupling of these systems is sensitive to chain length and termination.

The Best Models of Bodipy's Electronic Excited State: Comparing Predictions from Various DFT Functionals with Measurements from Femtosecond Stimulated Raman Spectroscopy.

Density functional theory (DFT) and time-dependent DFT (TD-DFT) are pivotal approaches for modeling electronically excited states of molecules. However, choosing a DFT exchange-correlation functional (XCF) among the myriad of alternatives is an overwhelming task that can affect the interpretation of results and lead to erroneous conclusions. The performance of these XCFs to describe the excited-state properties is often addressed by comparing them with high-level wave function methods or experimentally available vertical excitation energies; however, this is a limited analysis that relies on evaluation of a single point in the excited-state potential energy surface (PES). Different strategies have been proposed but are limited by the difficulty of experimentally accessing the electronic excited-state properties. In this work, we have tested the performance of 12 different XCFs and TD-DFT to describe the excited-state potential energy surface of Bodipy (2,6-diethyl-1,3,5,7-tetramethyl-8-phenyldipyrromethene difluoroborate). We compare those results with resonance Raman spectra collected by using femtosecond stimulated Raman spectroscopy (FSRS). By simultaneously fitting the absorption spectrum, fluorescence spectrum, and all of the resonance Raman excitation profiles within the independent mode displaced harmonic oscillator (IMDHO) formalism, we can describe the PES at the Franck-Condon (FC) region and determine the solvent and intramolecular reorganization energy after relaxation. This allows a direct comparison of the TD-DFT output with experimental observables. Our analysis reveals that using vertical absorption energies might not be a good criterion to determine the best XCF for a given molecular system and that FSRS opens up a new way to benchmark the excited-state performance of XCFs of fluorescent dyes.

Study on Asymmetric Vibrational Coherent Magnetic Transitions and Origin of Fluorescence in Symmetric Structures.

In this work, the physical mechanisms of three highly efficient circularly polarized luminescent materials are introduced. The UV-vis spectra are plotted; the transition properties of their electrons at the excited states are investigated using a combination of the transition density matrix (TDM) and the charge difference density (CDD); combining the distribution of electron clouds, the essence of charge transfer excitation in three structures is explained. The resonance Raman spectrum of the three structures at the S1 and S2 excited states are calculated. The M, M-4 and M, M-5 structures are found to produce novel chirality by electronic circular dichroism (ECD) spectrum, and the reasons for the chirality of the M, M-4 and M, M-5 structures are discussed by analyzing the density of transition electric/magnetic dipole moments (TEDM/TMDMs) in different orientations. Finally, the Raman optical activity (ROA) of M, M-4, and M, M-5 are calculated, and the spectra are plotted. This study will provide guidance for the application of carbon-based nanomaterials in organic electronic devices, solar cells, and optoelectronics.

Raman Spectroscopy of Formamidinium-Based Lead Mixed-Halide Perovskite Bulk Crystals.

In recent years, there has been an impressively fast technological progress in the development of highly efficient lead halide perovskite solar cells. Nonetheless, the stability of perovskite films and associated solar cells remains a source of uncertainty and necessitates sophisticated characterization techniques. Here, we report low- to mid-frequency resonant Raman spectra of formamidinium-based lead mixed-halide perovskites. The assignment of the different Raman lines in the measured spectra is assisted by DFT simulations of the Raman spectra of suitable periodic model systems. An important result of this work is that both experiment and theory point to an increase of the stability of the perovskite structure with increasing chloride doping concentration. In the Raman spectra, this is reflected by the appearance of new lines due to the formation of hydrogen bonds. Thus, higher chloride doping results in less torsional motion and lower asymmetric bending contributing to higher stability. This study yields a solid basis for the interpretation of the Raman spectra of formamidinium-based mixed-halide perovskites, furthering the understanding of the properties of these materials, which is essential for their full exploitation in solar cells.

Resonance Raman spectra and excited state properties of methyl viologen and its radical cation from time-dependent density functional theory.

Time-dependent density functional theory (TDDFT) was applied to gain insights into the electronic and vibrational spectroscopic properties of an important electron transport mediator, methyl viologen (MV2+ ). An organic dication, MV2+ has numerous applications in electrochemistry that include energy conversion and storage, environmental remediation, and chemical sensing and electrosynthesis. MV2+ is easily reduced by a single electron transfer to form a radical cation species (MV•+ ), which has an intense UV-visible absorption near 600 nm. The redox properties of the MV2+ /MV•+ couple and light-sensitivity of MV•+ have made the system appealing for photo-electrochemical energy conversion (e.g., solar hydrogen generation from water) and the study of photo-induced charge transfer processes through electronic absorption and resonance Raman spectroscopic measurements. The reported work applies leading TDDFT approaches to investigate the electronic and vibrational spectroscopic properties of MV2+ and MV•+ . Using a conventional hybrid exchange functional (B3-LYP) and a long-range corrected hybrid exchange functional (ωB97X-D3), including with a conductor-like polarizable continuum model to account for solvation, the electronic absorption and resonance Raman spectra predicted are in good agreement with experiment. Also analyzed are the charge transfer character and natural transition orbitals derived from the TDDFT vertical excitations calculated. The findings and models developed further the understanding of the electronic properties of viologens and related organic redox mediators important in renewable energy applications and serve as a reference for guiding the interpretation of electronic absorption and Raman spectra of the ions.

Resonance Raman spectra of blue copper proteins: Variable temperature spectra of Thermus thermophilus HB27 laccase

The resonance Raman (rR) spectra of the oxidized type 1 copper active site (CuT1) in Thermus thermophilus HB27 laccase (Tth-lac) has been determined in the 20 to 80 °C temperature range using 633-nm excitation. The positions and relative intensities of rR peaks are virtually independent of temperature, indicating that CuT1 ligation is robust over the investigated range. The intensity-weighted average of Tth-lac Cu-SCys vibrations (<ν(Cu-SCys)>) = 423 cm−1) is higher than those of most cupredoxins but is comparable to those of other multicopper oxidases (MCOs). <ν(Cu-SCys)> values for Tth-lac and several CuT1 centers in cupredoxins and MCOs do not correlate well with Cu-SCys bond lengths but do exhibit systematic trends with redox thermodynamic properties. PrologueF. Ann Walker was a great scholar and dear friend. While at Columbia in the early 1960s, I (HBG) followed her graduate work at Brown on the effects of axial ligands on vanadyl ion EPR spectra. Dick Carlin, her thesis adviser, invited me to serve as external member of her thesis committee. I joined, made my way to Providence, met her just before the exam, and greatly admired (enjoyed!) her thoughtful responses to questions from physical chemists about metal-oxo electronic structures. Our friendship grew stronger over the years, enhanced by lively discussions of heme protein chemistry in San Francisco, Pasadena, Tucson, and at Gordon Research Conferences. Ann was a superstar in biological inorganic chemistry. She will be sorely missed but not forgotten.

Stimulated Resonance Raman and Excited-State Dynamics in an Excitonically Coupled Bodipy Dimer: A Test for TD-DFT and the Polarizable Continuum Model.

Bodipy is one of the most versatile and studied functional dyes due to its myriad applications and tunable spectral properties. One of the strategies to adjust their properties is the formation of Bodipy dimers and oligomers whose properties differ significantly from the corresponding monomer. Recently, we have developed a novel strategy for synthesizing α,α-ethylene-bridged Bodipy dimers; however, their excited-state dynamics was heretofore unknown. This work presents the ultrafast excited-state dynamics of a novel α,α-ethylene-bridge Bodipy dimer and its monomeric parent. The dimer's steady-state absorption and fluorescence suggest a Coulombic interaction between the monomeric units' transition dipole moments (TDMs), forming what is often termed a "J-dimer". The excited-state properties of the dimer were studied using molecular excitonic theory and time-dependent density functional theory (TD-DFT). We chose the M06 exchange-correlation functional (XCF) based on its ability to reproduce the experimental oscillator strength and resonance Raman spectra. Ultrafast laser spectroscopy reveals symmetry-breaking charge separation (SB-CS) in the dimer in polar solvents and the subsequent population of the charge-separated ion-pair state. The charge separation rate falls into the normal regime, while the charge recombination is in the inverted regime. Conversely, in nonpolar solvents, the charge separation is thermodynamically not feasible. In contrast, the monomer's excited-state dynamics shows no dependence on the solvent polarity. Furthermore, we found no evidence of significant structural rearrangement upon photoexcitation, regardless of the deactivation pathway. After an extensive analysis of the electronic transitions, we concluded that the solvent fluctuations in the local environment around the dimer create an asymmetry that drives and stabilizes the charge separation. This work sheds light on the charge-transfer process in this new set of molecular systems and how excited-state dynamics can be modeled by combining the experiment and theory.

Molecular Interactions Identified by Two-Dimensional Analysis-Detailed Insight into the Molecular Interactions of the Antimalarial Artesunate with the Target Structure β-Hematin by Means of 2D Raman Correlation Spectroscopy.

A thorough understanding of the interaction of endoperoxide antimalarial agents with their biological target structures is of utmost importance for the tailored design of future efficient antimalarials. Detailed insights into molecular interactions between artesunate and β-hematin were derived with a combination of resonance Raman spectroscopy, two-dimensional correlation analysis, and density functional theory calculations. Resonance Raman spectroscopy with three distinct laser wavelengths enabled the specific excitation of different chromophore parts of β-hematin. The resonance Raman spectra of the artesunate-β-hematin complexes were thoroughly analyzed with the help of high-resolution and highly sensitive two-dimensional correlation spectroscopy. Spectral changes in the peak properties were found with increasing artesunate concentration. Changes in the low-frequency, morphology-sensitive Raman bands indicated a loss in crystallinity of the drug-target complexes. Differences in the high-wavenumber region were assigned to increased distortions of the planarity of the structure of the target molecule due to the appearance of various coexisting alkylation species. Evidence for the appearance of high-valent ferryl-oxo species could be observed with the help of differences in the peak properties of oxidation-state sensitive Raman modes. To support those findings, the relaxed ground-state structures of ten possible covalent mono- and di-meso(Cm)-alkylated hematin-dihydroartemisinyl complexes were calculated using density functional theory. A very good agreement with the experimental peak properties was achieved, and the out-of-plane displacements along the lowest-frequency normal coordinates were investigated by normal coordinate structural decomposition analysis. The strongest changes in all data were observed in vibrations with a high participation of Cm-parts of β-hematin.

Cluster structure of ultrahard fullerite revealed by Raman spectroscopy

We have discovered Raman peculiarities of sp3-bonded carbon nanoclusters forming ultrahard fullerite synthesized at pressure up to 85 GPa. The nanoclusters differ in the values of bulk modulus B0 ranging from 580 to 730 GPa. We found that the Raman frequency, corresponding to the C-C stretching mode of the nanoclusters, varies linearly from 1485 to 1640 cm−1, depending on the excitation wavelength used, which ranges from 785 nm to 257 nm. In particular, the nanoclusters with higher B0 have a higher Raman frequency. We also observed a resonant Raman spectrum when excited at a wavelength of 1064 nm. This showed a plateau from 1400 to 1720 cm−1, covering all Raman band positions of the nanoclusters from 1485 to 1640 cm−1. In addition, two Raman bands at 1285 and 1600 cm−1 appear at the resonance. The presence of several types of carbon sp3-bonded nanoclusters is confirmed by high-resolution transmission electron microscopy. Using moment tensor potentials, a class of machine learning interatomic potentials, we calculated the phonon density of states of the nanoclusters formed during the 3D polymerization of C60. The presence of high frequency modes in the resonant Raman spectra suggests the existence of bonds with force constants higher than those in a single crystal diamond. In addition, we observed a stiffening effect when analyzing the dependence of the mechanical stiffness on the cluster size, with smaller clusters exhibiting a more rigid structure.

Characterization of Secondary Structures of Model Polypeptides in Solutions with Hyper-Raman Spectroscopy.

Characterization of the secondary structures of two model polypeptides, poly-l-lysine and poly-l-glutamic acid in aqueous solutions has been demonstrated by hyper-Raman (HR) spectroscopy for the first time. Complementary to infrared (IR) and visible Raman spectroscopy, HR spectroscopy gives the amide I, II, and III bands originating from the polypeptide backbones and the CCH3 symmetric bending mode, enabling us to distinguish different conformations. The α-helix gives the broad and weak amide III band, while the β-sheet and the random coil show similar spectral patterns with different relative intensities between the amide I and II bands. HR spectra from aqueous solutions of the α-helix and the random coil of poly-l-ornithine also possess these spectral features. The HR spectra are analogous to UV resonance Raman (UVRR) spectra, indicating the signal enhancement due to the electronic resonance effect via the π-π* transition. In contrast, the vibrational frequencies of the amide I band in the HR spectra are much higher than those in the IR, visible Raman, and UVRR spectra, suggesting the non-coincidence between HR, IR, and Raman bands. Our finding suggests that HR spectroscopy is promising to provide complementary information on the secondary structures of polypeptides in aqueous solutions as a spectral approach differing from existing vibrational spectroscopic methods.

Effects of magnetite on nitrate-dependent anaerobic oxidation of methane in an anaerobic membrane biofilm reactor: Metatranscriptomic analysis and mechanism prediction

Magnetite has been widely reported to accelerate methane production in anaerobic digestion. However, the effects of magnetite on the process of methane consumption, specifically nitrate-dependent anaerobic oxidation of methane (AOM), and its underlying mechanisms remain poorly understood. In this study, the addition of magnetite significantly improved the removal of nitrate in an anaerobic membrane biofilm reactor (AnMBfR) (25.2 ± 2.5 mg NO3−-N/L/d) compared to that in an AnMBfR without magnetite (8.7 ± 4.2 mg NO3−-N/L/d). Metatranscriptomic analysis showed that genes encoding type IV pilus assembly proteins were highly expressed in nitrate/nitrite-reducing bacteria in the biofilms of the two AnMBfRs. Specifically, the transcript abundance of these genes was observed to be higher in the presence of magnetite (gene expression levels, log2FPKM = 13.08) compared to the absence of magnetite (12.04). Biofilms with magnetite exhibited a linear increase in electron transfer resistance with increasing temperature, and the decrease in pH significantly increased their conductivity, indicating a metallic-like conductivity. Contrarily, an increase in temperature or decrease in pH did not influence the resistance or conductivity of biofilms without magnetite. Some of these cytochrome c (CYC)-like proteins were electrically active in the electrochemical Fourier transform infrared spectra and were closely associated with the outer-membrane multi-heme c-type cytochromes (OMCs). The intensities of the OMC-like bands in the surface-enhanced resonance Raman spectra with biofilms in the presence of magnetite were higher than those without magnetite. This study suggests that magnetite promotes the nitrate-dependent AOM process because of the formation of methanotrophic consortia based on direct interspecies electron transfer (DIET).

Quasi-classical simulations of resonance Raman spectra based on path integral linearization.

Based on a linearization approximation coupled with path integral formalism, we propose a method derived from the propagation of quasi-classical trajectories to simulate resonance Raman spectra. This method is based on ground state sampling followed by an ensemble of trajectories on the mean surface between the ground and excited states. The method was tested on three models and compared to a quantum mechanics solution based on a sum-over-states approach: harmonic and anharmonic oscillators and the HOCl molecule (hypochlorous acid). The method proposed is able to correctly characterize resonance Raman scattering and enhancement, including the description of overtones and combination bands. The absorption spectrum is obtained at the same time, and the vibrational fine structure can be reproduced for long excited state relaxation times. The method can also be applied to dissociating excited states (as is the case for HOCl).

Ultraviolet Resonance Raman Spectra of Serum Albumins.

The ultraviolet resonance Raman (UVRR) spectra of the two proteins bovine serum albumin (BSA) and human serum albumin (HSA) in an aqueous solution are compared with the aim to distinguish between them based on their very similar amino acid composition and structure and to obtain signals from tryptophan that has only very few residues. Comparison of the protein spectra with solutions of tryptophan, tyrosine, and phenylalanine in comparative ratios as in the two proteins shows that at an excitation wavelength of 220 nm, the spectra are dominated by the strong resonant contribution from these three amino acids. While the strong enhancement of two and one single tryptophan residue in BSA and HSA, respectively, results in pronounced bands assigned to fundamental vibrations of tryptophan, its weaker overtones and combination bands do not play a major role in the spectral range above 1800 cm-1. There, the protein spectra clearly reveal the signals of overtones and combination bands of phenylalanine and tyrosine. Assignments of spectral features in the range of Raman shifts from 3800 to 5100 cm-1 to combinations comprising fundamentals and overtones of tyrosine were supported by spectra of amino acid mixtures that contain deuterated tyrosine. The information in the high-frequency region of the UVRR spectra could provide information that is complementary to near-infrared absorption spectroscopy of the proteins.

Resonance Raman Spectra and Structures of Ni-Complexes of Octaalkylporphyrins in the Ground and Excited States

Resonance Raman Spectra and Structures of Ni-Complexes of Octaalkylporphyrins in the Ground and Excited States