Internal Conversion Channel Research Articles

Deuterium Isotope Effect in Single Molecule Photophysics and Photochemistry of Hypericin.

The peripherical protons of the dye molecule hypericin can undergo structural interconversion (tautomerization) between different isomers separated by a low energy barrier with rates that depends sensitively on the interaction with local chemical environment defined by the nature of host material. We investigate the deuterium (D) isotope effect of hypericin tautomerism at the single-molecule level to avoid ensemble averaging in different polymer matrices by a combined spectroscopic and computational approach. In the 'innocent' PMMA matrix only intramolecular isotope effects on the internal conversion channel and tautomerization are observed; while PVA specifically interacts with the probe via H- and D-bonding. This establishes a single molecular picture on intra- and intermolecular nano-environment effects to control chromophore photophysics and -chemistry.

Photodynamics of azaindoles in polar media: the influence of the environment.

We have studied the relaxation dynamics of a family of azaindole (AI) structural isomers, 4-, 5-, 6- and 7-AI, by steady-state and time-resolved methods (fs-transient absorption and fluorescence up-conversion), in solvents of different polarity. The measurements in aprotic solvents show distinctive fluorescence yields and excited state lifetimes among the isomers, which are tuned by the polarity of the medium. Guided by simple TD-DFT calculations and based on the behavior observed in the isolated species, it has been possible to address the influence of the environment polarity on the relaxation route. According to the obtained picture, the energy of the nπ* state, which is strongly dependent on the position of the pyridinic nitrogen, controls the rate of the internal conversion channel that accounts for the distinctive photophysical behavior of the isomers. On the other hand, preliminary measurements in protic media (methanol) show a very different photodynamical behavior, in which the anomalous measured fluorescent patterns are very likely the result of reactive channels (proton transfer) triggered by the electronic excitation.

Tuning the competition between photoisomerization and photothermy in biomimetic cyclocurcumin analogues

We report the synthesis and photophysical characterization of biomimetic D-A-D’ cyclocurcumin derivatives, which can potentially be used in light activated chemotherapy. Particularly we highlight that both the donor (D) and acceptor (A) groups significantly influence the photophysical response of the chromophore inducing strong bathochromic shift with D/A strength increase and notable fluorescence quantum yield enhancement with donor strength increase. More important, the nature of the acceptor group (oxo or malonitrile) dramatically modifies the outcome in non-radiative deactivation channels. Indeed, while compounds functionalized with an oxo-moiety undergo ethylenic E → Z photoisomerization, the one bearing a malonitrile group leads exclusively to other non-adiabatic internal conversion channels which much favor photothermal conversion as no isomerization of the ethylenic double bond was observed. The tuning of the photophysical properties and the alteration of isomerization vs photothermal conversion is rationalized through the analysis of the potential energy surfaces along the most relevant degrees of freedom and shows a competitive pathway over malonitrile rotation. Our results offer novel perspective in oxygen-independent light activated chemotherapy and in the control of photochemical processes in biomimetic chromophores.

Quantum mechanics/molecular mechanics studies on the excited-state decay mechanisms of cytidine aza-analogues: 5-azacytidine and 2'-deoxy-5-azacytidine in aqueous solution.

The excited state properties and deactivation pathways of two DNA methylation inhibitors, i.e., 5-azacytidine (5ACyd) and 2'-deoxy-5-azacytidine (5AdCyd) in aqueous solution, are comprehensively explored with the QM(CASPT2//CASSCF)/MM protocol. We systematically map the feasible decay mechanisms based on the obtained excited-state decay paths involving all the identified minimum-energy structures, conical intersections, and crossing points driving the different internal conversion (IC) and intersystem crossing (ISC) routes in and between the 1ππ*, 1nπ*, 3ππ*, 3nπ*, and S0 states. Unlike the 1nπ* state below the 1ππ* state in 5ACyd, deoxyribose group substitution at the N1 position leads to the 1ππ* state becoming the S1 state in 5AdCyd. In 5ACyd and 5AdCyd, the initially populated 1ππ* state mainly deactivates to the S0 state through the direct 1ππ* → S0 IC or mediated by the 1nπ* state. The former nearly barrierless IC channel of 1ππ* → S0 occurs ultrafast via the nearby low-lying 1ππ*/S0 conical intersection. In the latter IC channel of 1ππ* → 1nπ* → S0, the initially photoexcited 1ππ* state first approaches the nearby S2/S1 conical section 1ππ*/1nπ* and then undergoes efficient IC to the 1nπ* state, followed by the further IC to the initial S0 state via the S1/S0 conical intersection 1nπ*/S0. The 1nπ*/S0 conical intersection is estimated to be located 6.0 and 4.9 kcal mol-1 above the 1nπ* state minimum in 5ACyd and 5AdCyd, respectively, at the QM(CASPT2)/MM level. In addition to the efficient singlet-mediated IC channels, the minor ISC routes would populate 1ππ* to T1(ππ*) through 1ππ* → T1 or 1ππ* → 1nπ* → T1. Relatively, the 1ππ* → 1nπ* → T1 route benefits from the spin-orbit coupling (SOC) of 1nπ*/3ππ* of 8.7 cm-1 in 5ACyd and 10.2 cm-1 in 5AdCyd, respectively. Subsequently, the T1 system will approach the nearby T1/S0 crossing point 3ππ*/S0 driving it back to the S0 state. Given the 3ππ*/S0 crossing point located above the T1 minimum and the small T1/S0 SOC, i.e., 8.4 kcal mol-1 and 2.1 cm-1 in 5ACyd and 6.8 kcal mol-1 and 1.9 cm-1 in 5AdCyd, respectively, the slow T1 → S0 would trap the system in the T1 state for a while. The present work could contribute to understanding the mechanistic photophysics and photochemistry of similar aza-nucleosides and their derivatives.

Computer‐Aided Design of Fluorinated Flavin Derivatives by Modulation of Intersystem Crossing and Fluorescence

AbstractThis study aims at finding fluorinated flavin derivatives with modified intersystem crossing (ISC) and fluorescence properties. In total, photophysical properties of 8 derivatives were investigated computationally using combined density functional theory and multireference configuration interaction methods. On top of a screening procedure, the excited‐state decay mechanisms of selected chromophores were investigated in detail. Kinetic schemes including fluorescence, ISC as well as internal conversion (IC) channels were set up to unravel the complex excited‐state decay kinetics. We find two chromophores that exhibit promising properties with respect to fluorescence microscopy. Distinctive stabilization of the brightππ* state results in absorption in the green wavelength region and emission of (infra‐)red light. The1(πHπL)⤳3(πH–1πL) ISC channel of the flavin chromophore was found to be deactivated upon both modifications, but nonradiative deactivation of the fluorescence by IC appears to be a problem. Alternative modifications of the pteridine dione moiety were found to result in a marked stabilization ofnπ* states along with activation of El‐Sayed allowed ISC channels. For the latter two compounds, we predict fluorescence to be quenched by ISC followed by efficient population of the long‐livedstate via IC.

Unveiling the photophysical, biomolecule binding and photo-oxidative capacity of novel Ru(II)-polypyridyl corroles: A multipronged approach

Two fluorinated corrole derivatives, namely H3MebpyCor and RuMebpyCor, were synthesized and characterized in terms of their photophysical, electrochemical, and photooxidation behavior. Their biomolecular binding capacity toward Human Serum Albumin (HSA) and calf thymus DNA (CT-DNA) was also evaluated. The experimental data were correlated with theoretical analysis via Time Dependent Density Functional Theory (TDDFT) and Molecular Docking calculations. We found an extremely low fluorescence quantum yield for both corroles dissolved in acetonitrile (CH3CN) and dimethyl sulfoxide (DMSO), which suggests a relaxation pathway through nonradiative processes, such as internal conversion. However, the internal conversion channel in RuMebpyCor competes with the energy transfer to the Ru(II) moiety, placing triplet state formation as a second mechanism of relaxation for this structure. Both corroles showed no aggregation and good photostability. The singlet oxygen (1O2) quantum yield (ΦΔ) values also highlight their potential application in photoinactivation approaches. Theoretical analysis suggests that the introduction of Ru(II) ion coordinated in the bipyridyl unit significantly alters the optically induced electronic transitions, and that the solvents play an important role in defining the optical spectra of the two corroles. Additionally, they interact spontaneously and moderate to strong via ground-state association (static process) with HSA and CT-DNA. However, for the HSA binding assays the dynamic fluorescence quenching mechanism can also occur at high corrole concentrations. Finally, in silico calculations suggest that the main binding region into CT-DNA is the minor groove, while subdomain IIA (site I) is the main binding region for HSA:H3MebpyCor (experimental proportion 1:1) and both subdomains IIA and IB (sites I and III, respectively) for HSA:RuMebpyCor (experimental proportion 1:2).

Prediction of the excited-state reaction channels in photo-induced processes of nitrofurantoin using first-principle calculations and dynamics simulations

The understanding of the photochemistry of antibiotic compounds is important because it gives the direct information on the possible environmental pollution caused by them. Due to their large size, the theoretical studies of their excited-state reactions are rather challenging. In current work, we combined the on-the-fly trajectory surface-hopping dynamics, conical-intersection optimizations and excited-state pathway calculations to study the photochemistry of the trans-isomer of nitrofurantoin, a widely-used drug to treat the urinary tract infections. The dynamics-then-pathway approach was taken. First the trajectory surface hopping dynamics at the state-averaged complete-active-space self-consistent-field (SA-CASSCF) level with small active space and small basis sets were run. Second, the minimum-energy conical-intersection optimizations were performed. Finally the excited pathways from the Frank-Condon region to different reaction channels were built at the multi-state multi-reference second-order perturbation (MS-CASPT2) level with large active space and large basis set. Several possible channels responsible for the photo-induced reaction mechanism of the trans-nitrofurantoin were obtained, including the cleavage of the NO bond of the NO2 moiety, the photoisomerization at the central CN bond, and other internal conversion channels. Our findings give some preliminary explanations on available experimental observations. It is also demonstrates that the current theoretical approach is a powerful tool to explore the excited-state reactions in the photochemistry of media-sized or large-sized drug compounds.

Ultrafast excited-state dynamics of promising nucleobase ancestor 2,4,6-triaminopyrimidine.

The ultrafast excited-state dynamics of 2,4,6-triaminopyrimidine - thought to be a promising candidate for a proto-RNA nucleobase - have been investigated via static multireference quantum-chemical calculations and mixed-quantum-classical/trajectory surface-hopping dynamics with a focus on the lowest-lying electronic states of the singlet manifold and with a view towards understanding the UV(C)/UV(B) photostability of the molecule. Ultrafast internal conversion channels have been identified that connect the lowest-lying ππ* electronically-excited state of 2,4,6-triaminopyrimidine with the ground electronic state, and non-radiative decay has been observed to take place on the picosecond timescale via a ππ* out-of-plane NH2 ("oop-NH2") minimum-energy crossing point. The short excited-state lifetime is competitive with the excited-state lifetimes of the canonical pyrimidine nucleobases, affirming the promise of 2,4,6-triaminopyrimidine as an ancestor. Evidence for energy-dependent excited-state dynamics is presented, and the open question of intersystem crossing is discussed speculatively.

Internal conversion of the low-energy Th229m isomer in the thorium anion

A process of the decay of the anomalously low lying nuclear isomer $^{229m}$Th$(3/2^+,8.28 \pm 0.17$ eV) in the Thorium anion (Th$^-$) via the internal conversion (IC) channel is studied. We show that the half life of the nuclear isomer in the $6d_{3/2}^37s_{1/2}^2$ ground state and in the $6d_{3/2}^2 7s_{1/2}^2 7p_{1/2}^1$ excited state of Th$^-$ is $\approx1.5$ and $\approx1.1$ times bigger than in the $6d_{3/2}^2 7s_{1/2}^2$ ground state of the Th atom. The IC probabilities in the anion decreases despite the decay via the additional $6d_{3/2}$ or $7p_{1/2}$ electrons. This counterintuitive result is a consequence: a) of a decrease in the amplitudes of the $6d_{3/2}$ and $7s_{1/2}$ wave functions near the nucleus due to an increase in their diffuseness of upon the addition of extra electron, b) of mutual compensation in the IC probability due to a kinematic factor, which depends on the energy of the conversion electron in the continuum as $E_c^{-1/2}$, and the $E_c^{1/4}$ growth of the amplitudes of the electron wave functions.

Toward Prediction of Nonradiative Decay Pathways in Organic Compounds II: Two Internal Conversion Channels in BODIPYs

Boron-dipyrromethene (BODIPY) molecules are widely used as laser dyes and have therefore become a popular research topic within recent years. Numerous studies have been reported for the rational de...

Ultrafast Fluorescence Signals from β-Dihydronicotinamide Adenine Dinucleotide: Resonant Energy Transfer in the Folded and Unfolded Forms.

β-Dihydronicotinamide adenine dinucleotide (NADH) plays a critical role in biological redox processes. Inside the cell, NADH can be in a folded or an unfolded conformation, depending on the chemical environment that surrounds it. It is known that selective excitation of adenine in NADH can induce energy transfer events from this nucleotide to the reduced nicotinamide chromophore. From the anticipated time scales, this process must compete with adenine's internal conversion channel, which is known to occur in the sub-picosecond time scale. In this work, we studied the dynamics of the excited states of both chromophores in NADH through the time resolution of the spontaneous emission from both nucleotides. Through these experiments, we extend the knowledge about the competition between the different photophysical channels both in the folded and unfolded states. The study involved the folded and unfolded states of NADH by experiments in water and methanol solutions. Our femtosecond fluorescence results were complemented by the first nuclear magnetic resonance through space magnetization transfer measurements on NADH, which establish the solvent-dependent folded versus unfolded states. We determined the dynamics of the excited states by direct excitation of dihydronicotinamide at 380 nm and adenine at 266 nm. From this, we were able to measure for the folded state, a time constant of 90 fs for energy transfer. Additionally, we determined that even in what is referred to as an unfolded state in methanol, non-negligible excitation transfer events do take place. Spontaneous emission anisotropy measurements were used in order to confirm the presence of a minor energy transfer channel in the methanol solutions where the unfolded state dominates.

Decay of the low-energy nuclear Th229m isomer via atomic Rydberg states

In the paper, a unique process of the decay of the $^{229m}\mathrm{Th}(3/{2}^{+},8.28\ifmmode\pm\else\textpm\fi{}0.17$ eV) low-energy nuclear isomer via the internal conversion (IC) channel on Rydberg states is considered for the first time. The Rydberg atom $^{229m}\mathrm{Th}^{+}+{e}_{Ry}^{\ensuremath{-}}$ is a unique object where IC is possible exclusively on the Rydberg electron ${e}_{Ry}^{\ensuremath{-}}$. It is shown that in the $^{229m}\mathrm{Th}^{4+}+{e}_{Ry}^{\ensuremath{-}}$ system (a) IC on the electron states with relatively small values of the principal quantum number $n$ and the orbital moment $l$ is practically completely suppressed, (b) IC probability, ${W}_{IC}$, on the ${\ensuremath{\psi}}_{n{s}_{1/2}}(\mathbf{r})$ states is proportional to $|{\ensuremath{\psi}}_{n{s}_{1/2}}{(0)|}^{2}$ and can be related with the energy of the hyperfine interaction of the Rydberg electron with the nucleus, (c) ${W}_{IC}$ decreases rapidly with the increase of $n$ in the range from 10 to 50, and in the range $n\ensuremath{\gtrsim}150\phantom{\rule{4pt}{0ex}}{W}_{IC}$ changes as $\text{const}/{n}^{3}$ typical for hydrogen-like ions, and (d) at $n\ensuremath{\approx}10$--30, ${W}_{IC}$ as a function of $l$ has a characteristic ``knee'' between $l=3$ and $l=4$, i.e., a decrease of three orders of magnitude in ${W}_{IC}$ due to the qualitative change in the ratio between the centrifugal and shielding potentials.

Excited State Decay Pathways of 2'-Deoxy-5-methylcytidine and Deoxycytidine Revisited in Solution: A Comprehensive Kinetic Study by Femtosecond Transient Absorption.

Methylated cytosine is proved to have an important role as an epigenetic signal in gene regulation and is often referred to "the fifth base of DNA". A comprehensive understanding of the electronic excited state relaxation in cytosine and its methylated derivatives is crucial for revealing UV-induced photodamage to the biological genome. Because of the existence of multiple closely lying "bright" and "dark" excited states, the decay pathways in these DNA nucleosides are the most complex and the least understood so far. In this study, femtosecond transient absorption with different excitation wavelengths (240-296 nm) was used to study the relaxation of excited electronic states of 5-methylcytosine (5mC) and 2'-deoxy-5-methylcytidine (5mdCyd) in phosphate buffered aqueous solution and in acetonitrile solution. Two distinct nonradiative decay channels were directly observed. The first one is a several picosecond internal conversion channel that involves two bright ππ* states (ππ*2 and ππ*1) when ππ*2 state is initially populated. The second channel contains the lower energy ππ*1 state and a so far experimental unidentified long-lived state which exhibits a several nanosecond lifetime. The long-lived state can only be accessed by the initially excited ππ*1 state. Inspired by this new discovery in 5mC and 5mdCyd, we revisited the decay of excited state of 2'-deoxycytidine (dCyd), revealing very similar decay pathways. Additionally, a well-known dark nOπ* state (carbonyl lone pair) with ∼30 ps lifetime is present in both decay channels in dCyd. With our detailed experimental results, we successfully reconcile the long history debate of cytosine excited state relaxation mechanism by pointing out that the reason for the complex dynamics under traditional 266 nm excitation is mixed signals from the above-mentioned two distinct decay pathways. Our findings lead to a dramatically different and new picture of electronic energy relaxation in 5mdCyd/dCyd and could help to understand photostability as well as UV-induced photodamage of these nucleotides and related DNAs.

Photoprotection or photodamage: a direct observation of nonradiative dynamics from 2-ethylhexyl 4-dimethylaminobenzoate sunscreen agent.

Apart from being an analogue of the prototype for photoinduced intramolecular charge transfer (ICT), 2-ethylhexyl 4-dimethylaminobenzoate (EHDMABA) is also one of the earliest patented and most commonly used sunscreen components. There is, however, little documented information about the photophysics and factors affecting the photophysics of this molecule. Such information is of importance for both the understanding of the ICT reaction and assessing the underlying process of photoprotection, especially in view of the "sunscreen controversy" that has arisen from the contrasting in vivo vs. in vitro photobiological results on this and related UV filters. We report herein a femtosecond broadband time-resolved fluorescence (fs-TRF), complemented by transient absorption (fs-TA) to allow a full probe of the excited state cascades for EHDMABA and two of its derivatives in solvents of varied properties. The results provide direct evidence for a nearly solvent independent inner sphere ICT reaction occurring on the sub-picosecond time scale, and an ensuing solvent dictated deactivation of the ICT state. The ICT state in the aprotic solvent acetonitrile decayed solely through the intrinsic intersystem crossing (ISC) to produce a potentially harmful triplet excited state. In the protic solvent, the solvation and formation of ICT-induced solute-solvent hydrogen (H)-bonding opened the originally inaccessible internal conversion (IC) channel of the ICT state, leading to the rapid reformation of the ground state molecule with a unitary efficiency in the aqueous solution. This H-bonding-mediated IC restrained or eliminated the intrinsic ISC, providing a mechanism at the molecular level for the benign dissipation of the electronic excitation. The precise rate of IC was observed to vary with the alkoxy substituent and its efficiency was affected by the H-bonding capacity of the solvent. The findings of this work demonstrate the pivotal role of the microenvironment and the direct participation of solvent molecules through H-bonding in drastically altering the nonradiative dynamics and promoting or inhibiting photostability and photoprotection. This may assist in developing next-generation UV filters and help in improving formulation design for the optimal efficacy of sunscreen products. The pronounced H-bonding-induced fluorescence quenching and variation in the fluorescence wavelength imply that these molecules may also serve as a sensitive fluorescence probe for the H-bonding properties of the microenvironment.

The influence of substituents of perylenediimides on their spectroscopic properties

The influence of substituents of newly synthesized perylenediimides on their spectral properties and excited state relaxation has been studied by means of steady-state and time-resolved spectroscopy and quantum chemical calculations. Substituents at the perylene core cause broadening and shift of the absorption and fluorescence bands and also reduce the fluorescence quantum yield. Organic 4-tert-butylphenoxy substituents reduce the fluorescence yield by tens of percent by slightly reducing the oscillator strength of the radiative transition and by significantly increasing the non-radiative decay rate. We attribute both changes mainly to the distortion of the planarity of the perylene core. Bromine substituents reduce the fluorescence quantum yield by up to two orders of magnitude by opening an internal conversion channel.

Quantum dynamical studies of ultrafast charge separation in nanostructured organic polymer materials: Effects of vibronic interactions and molecular packing

AbstractWe review recent work employing high‐dimensional quantum dynamical techniques to study ultrafast charge separation in functional organic materials, in view of understanding the key microscopic factors that lead to efficient charge generation in photovoltaics applications. As highlighted by recent experiments, these processes can be guided by quantum coherence, despite the presence of static and dynamic disorder. The present approach combines first‐principles parametrized lattice Hamiltonians, based on Time‐Dependent Density Functional Theory (TDDFT) and/or high‐level electronic structure calculations, with accurate quantum dynamics simulations using the Multi‐Configuration Time‐Dependent Hartree (MCTDH) method. This contribution specifically addresses the mechanism of charge generation in (i) regioregular oligothiophene‐fullerene aggregates, and (ii) highly ordered oligothiophene‐perylene diimide co‐oligomer assemblies. These studies highlight that chemical design of donor–acceptor combinations needs to account for the effects of electronic delocalization and the modified energetics due to molecular packing, as well as multiple transfer pathways and internal conversion channels induced by vibronic interactions.

The Coumarin-Dimer Spring-The Struggle between Charge Transfer and Steric Interactions.

The synthesis of a weakly coupled, strongly polarized coumarin dimer has been achieved for the first time. The three-step strategy comprises the Skattebøl formylation followed by the Knoevenagel reaction and the formation of a tertiary amide by using a peptide-type procedure. The molecule consists of two different coumarin moieties: One is a classical donor-acceptor system and the second one possesses a weaker amide donor at the 7-position. The polarized coumarin dimer can form an electronically conjugated structure possessing an electric dipole larger than that of 7-(dimethylamino)coumarin-3-carboxylic acid. The limited flexibility of the inter-coumarin connection results in stable conformers of different electric dipole moments and complex photophysics. In the solid state, this compound has a strongly bent conformation with the two coumarin units forming an angle of around 74°. In solution, two conformers are in equilibrium. The existence of the molecule as two conformers in the ground state has been confirmed by optical studies, and further corroborated by molecular calculations. The fluorescence spectra possess a unique feature: A charge-transfer band (ca. 550 nm) is visible only in nonpolar or weakly polar solvents. Optical spectroscopy studies coupled with molecular calculations allowed us to rationalize this phenomenon: The large amplitude of intramolecular motions is responsible for the conformational isomerization as well as producing a conical intersection between the potential energy surfaces of the excited singlet state and the ground state, which opens an internal conversion channel that effectively competes with the fluorescence of the conformers.

Reduced Transition Probabilities for the Gamma Decay of the 7.8eV Isomer in ^{229}Th.

The reduced magnetic dipole and electric quadrupole transition probabilities for the radiative decay of the ^{229}Th 7.8 eV isomer to the ground state are predicted within a detailed nuclear-structure model approach. We show that the presence and decay of this isomer can only be accounted for by the Coriolis mixing emerging from a remarkably fine interplay between the coherent quadrupole-octupole motion of the nuclear core and the single-nucleon motion within a reflection-asymmetric deformed potential. We find that the magnetic dipole transition probability which determines the radiative lifetime of the isomer is considerably smaller than presently estimated. The so-far disregarded electric quadrupole component may have non-negligible contributions to the internal conversion channel. These findings support new directions in the experimental search of the ^{229}Th transition frequency for the development of a future nuclear frequency standard.

Ultrafast energy transfer with competing channels: Non-equilibrium Förster and Modified Redfield theories.

We derive equations of motion for the reduced density matrix of a molecular system which undergoes energy transfer dynamics competing with fast internal conversion channels. Environmental degrees of freedom of such a system have no time to relax to quasi-equilibrium in the electronic excited state of the donor molecule, and thus the conditions of validity of Förster and Modified Redfield theories in their standard formulations do not apply. We derive non-equilibrium versions of the two well-known rate theories and apply them to the case of carotenoid-chlorophyll energy transfer. Although our reduced density matrix approach does not account for the formation of vibronic excitons, it still confirms the important role of the donor ground-state vibrational states in establishing the resonance energy transfer conditions. We show that it is essential to work with a theory valid in a strong system-bath interaction regime to obtain correct dependence of the rates on donor-acceptor energy gap.

Fluorescence of the lactone form of rhodamine B

A quantum-chemical investigation of spectral fluorescent properties of the lactone form of rhodamine B molecule is conducted with allowance for its interaction with polar solvent. It is shown that within the model, two emitting states emerge that can be attributed to the zwitterion and lactone forms of the rhodamine molecule based on their nature and energy. A lack of interaction between the emitting states is observed in the internal conversion channel. The rate constants of photophysical processes are estimated. The quantum yields of dual fluorescence are calculated.