IR Transitions Research Articles

Low Ir-Containing Materials As Anode Catalysts for PEM Water Electrolysis

The PEM electrolysis is based on the application of IrO2 as anode catalyst. Until now, there is no real alternative for this electrocatalyst, since the highly acidic and oxidative conditions at the anode lead to rapid corrosion.[1-3] With steadily increasing energy consumption, the demand for iridium will exceed the available resources in a few decades. As a result, the price of iridium as well as the technologies based on it will continuously increase. An enhancement of PEM electrolysis capacities on a large scale can therefore only be realized in the long term if the application of iridium is significantly reduced.[4] Therefore, our research aims at reducing the iridium content of PEM anodes while maintaining catalytic activity and stability.In this work, two approaches to save iridium were applied. On the one hand the iridium content was reduced by supporting it, on the other hand an additional, readily available metal is incorporated that is protected from corrosion by the presence of iridium and at the same time assists the iridium in catalysis.So, bimetallic included low-loading Ir and different transition metal (Ru, Sn, and Ag) nanoparticles on titanium nitride (TiN) were synthesized by using a chemical reduction method and thermal treatment. Experimentally, a IrSnOx/TiN sample in 0.5 M H2SO4 with an Ir loading of 0.05 mgIr/cm2 achieves a mass activity of over 450 A/gIr at 1.6 V vs RHE and an overpotential of 297 mV at 10 mA/cm2. The investigation includes stability tests at constant current density of 10 mA/cm2 and determination of impedance by electrochemical impedance spectroscopy (EIS).As result, a suitable anode material was successfully achieved, which exhibits a similarly good activity and stability values compared to the IrO2 materials that have been used industrially so far, but with a significantly reduction of iridium to 24% of the usually applied amount.[1] C. Minke, M. Suermann, B. Bensmann, R.H. Rauschenbach, Int. J. Hydrog. Energy, 2021, 46, 23581-23590.[2] F. Scarpelli, N. Godbert, A. Crispini, I. Aiello, Inorganics, 2022, 10, 115.[3] J. Gao, Y. Liu, B. Liu, K.W. Huang, ACS Nano, 2022, 16, 17761-17777.[4] T. Reier, H. N. Nong, D. Teschner, R. Schlögl, P. Strasser, Adv. Energy Mater., 2017, 7, 1601275.

Excited-State Symmetry Breaking and Localization in a Noncentrosymmetric Electron Donor-Acceptor-Donor Molecule.

Electronic excitation in quadrupolar conjugated molecules rapidly localizes on a single electron donor-acceptor (DA) branch when in polar environments. The loss of center of inversion upon this excited-state symmetry breaking (ES-SB) can be monitored by exploiting the relaxation of the exclusion rules for IR and Raman vibrational transitions. Here, we compare ES-SB in a right-angled (1) and a centrosymmetric (2) DAD dyes using time-resolved IR spectroscopy. We show that the localization of the excitation can also be identified with the bent molecule 1. We find that contrary to dye 2, subpopulations with localized and delocalized excitation coexist for 1 in weak to medium polar solvents. This difference originates from the torsional disorder present in the excited state of 1 but not of 2. Additionally, irreversible localization in a bent molecule is shown to require higher solvent polarity than in a centrosymmetric one.

A time averaged semiclassical approach to IR spectroscopy.

We propose a new semiclassical approach to the calculation of molecular IR spectra. The method employs the time averaging technique of Kaledin and Miller upon symmetrization of the quantum dipole-dipole autocorrelation function. Spectra at high and low temperatures are investigated. In the first case, we are able to point out the possible presence of hot bands in the molecular absorption line shape. In the second case, we are able to reproduce accurate IR spectra as demonstrated by a calculation of the IR spectrum of the water molecule, which is within 4% of the exact intensity. Our time averaged IR spectra can be directly compared to time averaged semiclassical power spectra as shown in an application to the CO2molecule, which points out the differences between IR and power spectra and demonstrates that our new approach can identify active IR transitions correctly. Overall, the method features excellent accuracy in calculating absorption intensities and provides estimates for the frequencies of vibrations in agreement with the corresponding power spectra. In perspective, this work opens up the possibility to interface the new method with the semiclassical techniques developed for power spectra, such as the divide-and-conquer one, to get accurate IR spectra of complex and high-dimensional molecular systems.

Dissolved gases analysis in transformer oil using TM (Pd, Ir, Au) modified MoSSe monolayer: A DFT study

This study applied density functional theory to investigate gas-sensitive devices based on transition metal-doped MoSSe (Pd-MoSSe, Ir-MoSSe, Au-MoSSe), exploring their adsorption and sensing performance towards three characteristic gases (CO, C2H2, C2H4) generated during the use or faults of transformer oil. The results indicate that Pd, Ir, and Au transition metal atoms preferentially anchor to the S surface of the pristine MoSSe monolayer. The doped monolayers exhibit significantly improved sensing characteristics in all aspects, suggesting chemical adsorption of the three characteristic gases. Through the analysis of band structures (BS), adsorption configurations, deformation charge densities (DCD), density of states (DOS), recovery time, and various adsorption parameters, the conclusion is drawn that while TM-MoSSe outperforms the pristine MoSSe monolayer in terms of adsorption and sensing performance, Pd-MoSSe and Au-MoSSe exhibit relatively good recovery times across a broader temperature range, whereas Ir-MoSSe is limited in this aspect. This study provides theoretical guidance for the potential application of transition metal-doped MoSSe monolayers as sensors for gases generated during the thermal runaway of transformer oil.

Aminoquinoline-based ruthenium(II) and iridium(III) polypyridyl complexes: Investigating potential photosensitisers for cancer treatment via photodynamic therapy

Cancer is a devastating noncommunicable disease that remains one of the most pressing health challenges of the twenty-first century. Chemotherapy stands as one of the most common and effective cancer treatment methods. However, severe side effects and acquired drug resistance in many cancers have significantly diminished the efficacy of current chemotherapeutic agents. The urgent demand for novel treatment modalities has led to the development of photodynamic therapy (PDT) for the treatment of various cancer types. In this work, the synthesis of aminoquinoline-based transition metal complexes containing two PGMs (Ir(III) and Ru(II)) as potential photosensitisers is described. Mononuclear N,N-chelated Ru(II) and Ir(III) transition metal complexes were synthesized by reacting 4-aminoquinoline Schiff base ligands, which contain either a pyridyl or a quinolyl entity. The photostable Ru(II) and Ir(III) polypyridyl complexes were investigated for their potential use as PDT agents. In vitro cytotoxicity screenings conducted against a melanoma cell line (501mel) both in the absence and presence of light confirmed that all complexes demonstrated increased biological activity when exposed to visible light at 455 nm. Overall, the Ru(II) complexes are superior phototoxic agents in comparison with their Ir(III) congenors.

Molecular Dihydrogen Activation by (C5Me5)M/N (M=Rh, Ir) Transition Metal Frustrated Lewis Pairs: Reversible Proton Migration to, and Proton Abstraction from, the C5Me5 Ligand.

The masked transition-metal frustrated Lewis pairs [Cp*M(κ3N,N',N''-L)][SbF6] (Cp*=η5-C5Me5; M=Ir, 1, Rh, 2; HL=pyridinyl-amidine ligand) reversibly activate H2 under mild conditions rendering the hydrido derivatives [Cp*MH(κ2N,N'-HL)][SbF6] observed as a mixture of the E and Z isomers at the amidine C=N bond (M=Ir, 3Z, 3E; M=Rh, 4Z, 4E). DFT calculations indicate that the formation of the E isomers follows a Grotthuss type mechanism in the presence of water. A mixture of Rh(I) isomers of formula [(Cp*H)Rh(κ2N,N'-HL)][SbF6] (5 a-d) is obtained by reductive elimination of Cp*H from 4. The formation of 5 a-d was elucidated by means of DFT calculations. Finally, when 2 reacts with D2, the Cp* and Cp*H ligands of the resulting rhodium complexes 4 and 5, respectively, are deuterated as a result of a reversible hydrogen abstraction from the Cp* ligand and D2 activation at rhodium.

Vibrational Dipole-Dipole Coupling and Long-Range Forces between Macromolecules.

Long-range interactions between biomacromolecules are considered important for directing intracellular processes. Recent studies have posited that interactions between oscillating dipoles are well-suited to mediating long-range forces because they are weakly screened by a dielectric environment. Here, we extend these studies and present a quantum electrodynamic mechanism for resonant interactions between vibrational transition dipole moments of molecules. We explicitly consider the molecular charge density oscillations as IR transition dipoles. This gives a physical, molecular assignment to the idea of oscillating dipoles and allows us to develop explicit expressions for the interactions that can be quantified using parameters known from experiment. Moreover, in the same framework, we can describe van der Waals forces. We use numerical calculations to estimate the strength of resonant vibrational dipole-dipole interactions over long distances and compare these estimates to the van der Waals interaction. We find that the resonant vibrational dipole-dipole interactions dominate over the long range.

Transient IR spectroscopy of optically centrifuged CO2 (R186-R282) and collision dynamics for the J = 244-282 states.

Collisions of optically centrifuged CO2 molecules with J = 244-282 (Erot = 22 800-30 300 cm-1) are investigated with high-resolution transient IR absorption spectroscopy to reveal collisional and orientational phenomena of molecules with hyper-thermal rotational energies. The optical centrifuge is a non-resonant optical excitation technique that uses ultrafast, 800 nm chirped pulses to drive molecules to extreme rotational states through sequential Raman transitions. The extent of rotational excitation is controlled by tuning the optical bandwidth of the excitation pulses. Frequencies of 30 R-branch ν3 fundamental IR probe transitions are measured for the J = 186-282 states of CO2, expanding beyond previously reported IR transitions up to J = 128. The optically centrifuged molecules have oriented angular momentum and unidirectional rotation. Polarization-sensitive transient IR absorption of individual rotational states of optically centrifuged molecules and their collision products reveals information about collisional energy transfer, relaxation kinetics, and dynamics of rotation-to-translation energy transfer. The transient IR probe also measures the extent of polarization anisotropy. Rotational energy transfer for lower energy molecules is discussed in terms of statistical models and a comparison highlights the role of increasing energy gap with J and angular momentum of the optically centrifuged molecules.

MOF-Derived CeO2 and CeZrOx Solid Solutions: Exploring Ce Reduction through FTIR and NEXAFS Spectroscopy.

The development of Ce-based materials is directly dependent on the catalyst surface defects, which is caused by the calcination steps required to increase structural stability. At the same time, the evaluation of cerium's redox properties under reaction conditions is of increasing relevant importance. The synthesis of Ce-UiO-66 and CeZr-UiO-66 and their subsequent calcination are presented here as a simple and inexpensive approach for achieving homogeneous and stable CeO2 and CeZrOx nanocrystals. The resulting materials constitute an ideal case study to thoroughly understand cerium redox properties. The Ce3+/Ce4+ redox properties are investigated by H2-TPR experiments exploited by in situ FT-IR and Ce M5-edge AP-NEXAFS spectroscopy. In the latter case, Ce3+ formation is quantified using the MCR-ALS protocol. FT-IR is then presented as a high potential/easily accessible technique for extracting valuable information about the cerium oxidation state under operating conditions. The dependence of the OH stretching vibration frequency on temperature and Ce reduction is described, providing a novel tool for qualitative monitoring of surface oxygen vacancy formation. Based on the reported results, the molecular absorption coefficient of the Ce3+ characteristic IR transition is tentatively evaluated, thus providing a basis for future Ce3+ quantification through FT-IR spectroscopy. Finally, the FT-IR limitations for Ce3+ quantification are discussed.

Pulsed inductive CO2 laser with radio-frequency excitation and influence of the H2 content on the efficiency and lasing temporal characteristics

In 2021, data on the effective pulsed gas discharge inductive CO2 laser with radio-frequency (RF) excitation were published with a pulse output energy of E∼ 1 J (the efficiency η∼ 14.5%) on the gas mixture He:N2:CO2 = 8:2:1. The efficiency of the developed CO2 laser had exceeded the value η∼ 21% at E∼ 350 mJ. At the beginning of 2022, it was shown that xenon addition (Xe = 4%) to the gas mixture made it possible to achieve an efficiency of η∼ 27% at an output energy of E∼ 600 mJ. For the first time, the effect of hydrogen additives in the active medium (He:N2:CO2:H2 and N2:CO2:H2 gas mixtures) was investigated for a pulsed inductive CO2 laser with RF excitation depending on the RF-pumping pulse duration value (τ), which allows the energy and temporal radiation characteristics of the laser to be controlled over a wider range. In addition to those already published, new experimental data have been obtained, namely the output beam profile of the inductive CO2 laser based on He:N2:CO2 = 8:2:1 gas mixture depending on the τ value. The new data will improve our understanding of inductive CO2 laser physics and of the plasma–chemical processes occurring in its active medium. RF current pulses propagated along inductor wires and, thus, an inductive discharge was formed to create a population inversion by IR transitions of CO2 * molecules.

The infrared features and full rotational constant catalogue of the newly detected MgC2 astromolecule

ABSTRACT The recent radioastronomical detection of magnesium dicarbide (MgC2) towards the carbon-rich star IRC+10216 leads to questions about whether this molecule can be observed in other wavelengths, especially with the wealth of IR data being produced by JWST. This present, theoretical spectral characterization, unfortunately, implies that mid-IR observations of MgC2 are unlikely due to small IR transition intensities, overlap with polycyclic aromatic hydrocarbon IR features, low frequencies/long wavelengths, or the relatively small column densities. In spite of this, the full set of fundamental anharmonic vibrational frequencies are provided for each of the 24Mg, 25Mg, and 26Mg isotopologues as are the complete rotational constants for the same set for additional laboratory characterization. Most notably and with regards to 24MgC2, the B0 and C0 (11452.7 and 9362.7 MHz) rotational constants are uniquely provided for the first time. The experimentally derived A0, (B + C)/2, and (B − C)/4 values are within 0.7 % of the presently computed anharmonic results implying similar accuracy for the remaining spectroscopic constants.

Photoexcitation of Nile blue dye in aqueous solution: TD-DFT study

The vibronic absorption spectra of Nile blue (NB) oxazine dye in an aqueous solution using 13 hybrid functionals, the 6-31++G(d,p) basis set, and the IEFPCM solvent model were calculated. It turned out that the O3LYP functional provided the best agreement with the experiment. Various parameters of the NB cation in the ground and excited states (IR spectra, atomic charges, dipole moments, and transition moment) were obtained. Maps of the distribution of electron density and electrostatic potential have been built. The influence of four strong hydrogen bonds of the dye with water molecules on the absorption spectrum was analyzed. It has been shown that two from these bonds were strengthened upon NB excitation and two ones were weakened. It was found that explicit assignment of water molecules strongly bound to the dye leads to a redshift of the spectrum as a whole and worsened its shape.

Bioactive Iridium Nanoclusters with Glutathione Depletion Ability for Enhanced Sonodynamic-Triggered Ferroptosis-Like Cancer Cell Death.

Ferroptosis is a regulated form of necrotic cell death that involves the accumulation of lipid peroxide (LPO) species in an iron- and reactive oxygen species (ROS)-dependent manner. Previous investigations have reportedthat ferroptosis-based cancer therapy can overcome the limitations of traditional therapeutics targeting the apoptosis pathway. However, it is still challenging to enhance the antitumor efficacy of ferroptosis due to intrinsic cellular regulation. In this study, a ferroptosis-inducing agent, i.e., chlorin e6 (Ce6)-conjugated human serum albumin-iridium oxide (HSA-Ce6-IrO2 , HCIr) nanoclusters, is developed to achieve sonodynamic therapy (SDT)-triggered ferroptosis-like cancer cell death. The sonosensitizing role of both Ce6 and IrO2 within the HCIr nanoclusters exhibits highly efficient 1 O2 generation capacity upon ultrasoundstimulation, which promotes the accumulation of LPO and subsequently induces ferroptosis. Meanwhile, the HCIr can deplete glutathione (GSH) by accelerating Ir (IV)-Ir (III) transition, which further suppresses the activity of glutathione peroxidase 4 (GPX4) to enhance the ferroptosis efficacy. Through in vitro and in vivo experiments, it is demonstrated that HCIr possesses tremendous capacity to reduce the intracellular GSH content, which enhances SDT-triggered ferroptosis-like cancer cell death. Thus, an iridium-nanoclusters-based ferroptosis-inducing agent is developed, providing a promising strategy for inducing ferroptosis-like cancer cell death.

Elucidating the Infrared Spectral Properties of Succinic Molecular Acid Crystals: Illustration of the Structure and the Hydrogen Bond Energies of the Crystal and Its Deuterated Analogs.

Herein, the infrared spectroscopic properties of molecular succinic acid crystals (SA) and their four isotopic analogs [C2H4(COOH)2, h6-SA; C2H4(COOD)2, d2-SA; C2D4(COOH)2, d4-SA; C2D4(COOD)2, d6-SA] are reported. The correlation between the structure of succinic acid molecules and their corresponding hydrogen bond energies is elucidated. The effects related to the isotopic dilution as well as the changes in the spectrum recording temperature on the fine structures of the vO-H and vO-D bands are interpreted. The infrared spectral anomalies detected in the spectra of isotopically neat succinic nanocrystal acids are confirmed by theoretical calculations using density functional theory (DFT). According to previous spectroscopic studies of succinic acid and those carried out for α,ω-dicarboxylic acids, a decent agreement between the experimental results and the theoretical DFT simulations is obtained. Moreover, the spectra of single crystals of the h6 and d4 succinic acid variants prove that the vibrational coupling mechanism between the (COOH)2 cycles is rigorously convergent to that detected in the spectra of aromatic carboxylic acids, suggesting thereby that the promotion of symmetry-forbidden high stretching IR transitions plays a crucial role. Furthermore, the obtained experimental results reveal that the succinic acid shows a spectral behavior significantly different from that characteristic of hydrogen associations of other acids of homologous series, such as the glutaric, adipic, malonic, and pimelic acid crystals. The results obtained herein shed light on the way to explore the revealed structure of isotopic derivatives of succinic acid crystals and may prove to be useful results for understanding the nature of unconventional interactions as well as the macroscopic energy effects directing the development of hydrogen associations.

Rapid Allylic 1,6 H-Atom Transfer in an Unsaturated Criegee Intermediate.

A novel allylic 1,6 hydrogen-atom-transfer mechanism is established through infrared activation of the 2-butenal oxide Criegee intermediate, resulting in very rapid unimolecular decay to hydroxyl (OH) radical products. A new precursor, Z/E-1,3-diiodobut-1-ene, is synthesized and photolyzed in the presence of oxygen to generate a new four-carbon Criegee intermediate with extended conjugation across the vinyl and carbonyl oxide groups that facilitates rapid allylic 1,6 H-atom transfer. A low-energy reaction pathway involving isomerization of 2-butenal oxide from a lower-energy (tZZ) conformer to a higher-energy (cZZ) conformer followed by 1,6 hydrogen transfer via a seven-membered ring transition state is predicted theoretically and shown experimentally to yield OH products. The low-lying (tZZ) conformer of 2-butenal oxide is identified based on computed anharmonic frequencies and intensities of its conformers. Experimental IR action spectra recorded in the fundamental CH stretch region with OH product detection by UV laser-induced fluorescence reveal a distinctive IR transition of the low-lying (tZZ) conformer at 2996 cm-1 that results in rapid unimolecular decay to OH products. Statistical RRKM calculations involving a combination of conformational isomerization and unimolecular decay via 1,6 H-transfer yield an effective decay rate keff(E) on the order of 108 s-1 at ca. 3000 cm-1 in good accord with the experiment. Unimolecular decay proceeds with significant enhancement due to quantum mechanical tunneling. A rapid thermal decay rate of ca. 106 s-1 is predicted by master-equation modeling of 2-butenal oxide at 298 K, 1 bar. This novel unimolecular decay pathway is expected to increase the nonphotolytic production of OH radicals upon alkene ozonolysis in the troposphere.

Photoexcitation of oxazine 4 dye in aqueous solution: TD-DFT study

The vibronic absorption spectra of oxazine 4 (OX4) dye in an aqueous solution using 40 hybrid functionals, the 6–31++G(d,p) basis set, and the SMD solvent model were calculated. It turned out that the X3LYP functional provided the best agreement with the experiment in the positions of the main maximum and the short-wavelength shoulder. Our calculations showed that this shoulder is vibronic and is not caused by a separate electronic transition. At the same time, the shoulder intensity in the calculated spectrum turned out to be lower than in the experimental one. Various parameters of the OX4 cation in the ground and excited states (IR spectra, atomic charges, dipole moments, and transition moment) were calculated. Maps of the distribution of electron density and electrostatic potential have been built. The influence of four strong hydrogen bonds of the dye with water molecules on the absorption spectrum was analyzed. It has been shown that these bonds were strengthened upon OX4 excitation. It was found that explicit assignment of water molecules strongly bound to the dye leads to a redshift of the spectrum as a whole, but does not change its shape. Photoexcitation of the dye leads to a noticeable polarization of only one of the four considered water molecules (associated with the endocyclic nitrogen atom in the central ring of the chromophore, the electron density on which increases the most).

The Ir-OOOO-Ir transition state and the mechanism of the oxygen evolution reaction on IrO2(110).

Carefully assessing the energetics along the pathway of the oxygen evolution reaction (OER), our computational study reveals that the “classical” OER mechanism on the (110) surface of iridium dioxide (IrO2) must be reconsidered. We find that the OER follows a bi-nuclear mechanism with adjacent top surface oxygen atoms as fixed adsorption sites, whereas the iridium atoms underneath play an indirect role and maintain their saturated 6-fold oxygen coordination at all stages of the reaction. The oxygen molecule is formed, via an Ir–OOOO–Ir transition state, by association of the outer oxygen atoms of two adjacent Ir–OO surface entities, leaving two intact Ir–O entities at the surface behind. This is drastically different from the commonly considered mono-nuclear mechanism where the O2 molecule evolves by splitting of the Ir–O bond in an Ir–OO entity. We regard the rather weak reducibility of crystalline IrO2 as the reason for favoring the novel pathway, which allows the Ir–O bonds to remain stable and explains the outstanding stability of IrO2 under OER conditions. The establishment of surface oxygen atoms as fixed electrocatalytically active sites on a transition-metal oxide represents a paradigm shift for the understanding of water oxidation electrocatalysis, and it reconciles the theoretical understanding of the OER mechanism on iridium oxide with recently reported experimental results from operando X-ray spectroscopy. The novel mechanism provides an efficient OER pathway on a weakly reducible oxide, defining a new strategy towards the design of advanced OER catalysts with combined activity and stability.

Vibronic absorption spectra and excited states of acridine red dye in aqueous solution: TD-DFT/DFT study

Abstract The vibronic absorption spectra of acridine red (AR) xanthene dye in an aqueous solution using 40 hybrid functionals, the 6-31++G(d,p) basis set, and the IEFPCM solvent model were calculated. It turned out that the O3LYP functional provided the best agreement with the experiment in the positions of the main maximum and the short-wavelength subband (shoulder). The calculations showed that this shoulder is vibronic. At the same time, the shoulder intensity in the calculated spectrum turned out to be lower than in the experimental one. Apparently, insignificant dimerization, which occurs even at low concentrations of the dye in solution, contributes to the shoulder of the experimental absorption spectrum. Various parameters of the AR cation in the ground and excited states (IR spectra, atomic charges, dipole moments, and transition moment) were calculated. Maps of the distribution of electron density and electrostatic potential have been built. The influence of the strong hydrogen bonds of the dye with three water molecules on the absorption spectrum was analyzed. It has been shown that these bonds are strengthened upon AR excitation. The strengthening of two hydrogen bonds with water upon excitation leads to a lowering of the potential energy surface of the excited state, which causes a decrease in the excitation energy (i.e., an increase in the wavelength of the absorbed photon) as compared to a purely implicit specification of the water environment. Therefore, explicit assignment of waters strongly bound to the dye leads to spectrum redshift.

Photoexcitation of brilliant cresyl blue dye in aqueous solution: TD-DFT study

The vibronic absorption spectra of brilliant cresyl blue (BCB) oxazine dye in an aqueous solution using 40 hybrid functionals, the 6-31++G(d,p) basis set, and the SMD solvent model were calculated. It turned out that the X3LYP functional provided the best agreement with the experiment in the positions of the main maximum and the short-wavelength shoulder. Our calculations showed that this shoulder is vibronic and is not caused by a separate electronic transition. At the same time, the shoulder intensity in the calculated spectrum turned out to be lower than in the experimental one. Various parameters of the BCB cation in the ground and excited states (IR spectra, atomic charges, dipole moments, and transition moment) were calculated. Maps of the distribution of electron density and electrostatic potential have been built. The influence of four strong hydrogen bonds of the dye with water molecules on the absorption spectrum was analyzed. It has been shown that these bonds are strengthened upon BCB excitation. It was found that explicit assignment of water molecules strongly bound to the dye leads to a redshift of the spectrum. Photoexcitation of the dye leads to a noticeable polarization of only one of the four considered water molecules.

Photoexcitation of methylene green dye in aqueous solution: TD-DFT study

The vibronic absorption spectra of methylene green (MG) thiazine dye in an aqueous solution using X3LYP hybrid functional, the 6-31++G(d,p) basis set, and the SMD solvent model were calculated. It turned out that this theory level the choice of which is based on previous theoretical studies of thiazine dyes provided excellent agreement with the experiment in the positions of the main maximum and the short-wavelength shoulder. Our calculations showed that this shoulder is vibronic and is not caused by a separate electronic transition. At the same time, the shoulder intensity in the calculated spectrum turned out to be lower than in the experimental one. Various parameters of the MG cation in the ground and excited states (IR spectra, atomic charges, dipole moments, and transition moment) were calculated. The dipole moment of the dye molecule in the ground state turned out to be the same as in the excited one, contrary to previous studies, where the dipole moment of a thiazine dyes without a nitro group increases upon excitation. This could be explained by the influence of the MG nitro group in position 6, due to which electron density increases on both diametrically opposite N10 and S5 atoms of the central ring. At the same time, in other thiazine dyes (without a nitro group), photoexcitation leads to a one-sided increase in the electron density at the N10 atom, and as a result, the projection of the dipole moment directed across the chromophore increases significantly. Maps of the distribution of electron density and electrostatic potential have been built. The influence of the strong hydrogen bonds of the dye with three water molecules on the absorption spectrum was analyzed. It has been shown that these bonds are strengthened upon MG excitation. It was found that explicit assignment of water molecules strongly bound to the dye leads to a redshift of the spectrum as a whole and worsened its shape.