Influence of Solvent Polarity and Hydrogen Bonding on the Electronic Transition of Coumarin 120: A TDDFT Study

The characteristics of the electronic transition energy of Coumarin 120 (C120) and its H‐bonded complexes in various solvents have been examined by time‐dependent density functional theory (TDDFT) in combination with a polarizable continuum solvent model (PCM). Molecular structures of C120 and its H‐bonded complexes are optimized with the B3LYP method in PCM solution, and the dihedral angle H14? N13? C7? H15 is dependent on solvent polarity and the type of H‐bond. A linear correlation of the absorption maximum of C120 with the solvent polarity function is revealed with the PCM model for all solvents except DMSO. The experimental absorption maximum of C120 in nine solvents is well described by a PCM–TDDFT scheme augmented with explicit inclusion of a few H‐bonded solvent molecules, and quantitative agreement between our calculated results and experimental measurements is obtained with an average error of less than 2 nm. H‐bonding at three different sites shifts the absorption wavelength of C120 either to the blue or to the red, that is, a significant role is played by solvent molecules in the first solvation shell in determining the electronic transition energy of C120. The dependence on the H‐bonding site and solvent polarity is examined by using the Kamlet–Taft equation for solvatochromism.     

Solvent effects on electronic structures and chain conformations of alpha-oligothiophenes in polar and apolar solutions

Solvent effects on electronic structures and chain conformations of alpha-oligothiophenes nTs (n = 1 to 10) are investigated in solvents of n-hexane, 1,4-dioxane, carbon tetrachloride, chloroform, and water by using density functional theory (DFT) and molecular dynamics (MD) simulations. Both implicit and explicit solvent models are employed. The polarized continuum model (PCM) calculations and MD simulations demonstrate the weak solvent effects on the electronic structures of alpha-oligothiophenes. The lowest dipole-allowed vertical excitation energies of nTs, obtained from time-dependent DFT/PCM calculations at the B3LYP/6-31G(d) level, exhibit a red shift as the solvent polarity increases, in agreement with experiments. The studied solvents have little impact on the state order of the low-lying excited states provided that the nTs are kept in C2h or C2v symmetry. The MD simulations demonstrate that the chain conformations are distorted to some extent in polar and nonpolar solvents. A qualitative picture of the distribution of solvent molecules around the solvated nTs is drawn by means of radial and spatial distribution functions. The S...H-O and pi...H-O solute-solvent interactions are insignificant in aqueous solution.     

Ab initio study of the solvent H-bonding effect on ESIPT reaction and electronic transitions of 3-hydroxychromone derivatives

The electronic transitions occurring in 4-(N,N-dimethylamino)-3-hydroxyflavone (DMAF) and 2-furanyl-3-hydroxychromone (FHC) were investigated using the TDDFT method in aprotic and protic solvents. The solvent effect was incorporated into the calculations via the PCM formalism. The H-bonding between solute and protic solvent was taken into account by considering a molecular complex between these molecules. To examine the effect of the H-bond on the ESIPT reaction, the absorption and emission wavelengths as well as the energies of the different states that intervene during these electronic transitions were calculated in acetonitrile, ethanol and methanol. The calculated positions of the absorption and emission wavelengths in various solvents were in excellent agreement with the experimental spectra, validating our approach. We found that in DMAF, the hydrogen bonding with protic solvents makes the ESIPT reaction energetically unfavourable, which explains the absence of the ESIPT tautomer emission in protic solvents. In contrast, the excited tautomer state of FHC remains energetically favourable in both aprotic and protic solvents. Comparing our calculations with the previously reported time-resolved fluorescence data, the ESIPT reaction of DMAF in aprotic solvents is reversible because the emitting states are energetically close, whereas in FHC, ESIPT is irreversible because the tautomer state is below the corresponding normal state. Therefore, the ESIPT reaction in DMAF is controlled by the relative energies of the excited states (thermodynamic control), while in FHC the ESIPT is controlled probably by the energetic barrier (kinetic control).     

Theoretical study of solvent influence on the electronic absorption and emission spectra of kynurenine

Neutral/zwitterionic form equilibrium, excited state wave functions, absorption and emission spectra of kynurenine (KN) in various solvents (water, methanol, ethanol, and dimethylsulfoxide) have been studied theoretically. The ground electronic state geometries have been optimized by density functional theory methods; the geometries of the first two singlets excited electronic states have been optimized using the CASSCF technique. The influence of the solvent was taken into account by the calculation of the solvation free energies using the Polarizable Continuum Model (PCM). The spectra of electronic absorption and fluorescence emission have been calculated by the CS‐INDO S‐CI and SDT‐CI methods [Momicchioli, Baraldi, and Bruni, Chem Phys, 1983, 82, 229]. The calculated data reproduce the experimental positions of maxima and the solvent‐induced shifts of the absorption and emission bands well. The energy gap between the two lowest excited states of KN increases from aprotic to protic solvents. This fact suggests that the “proximity effect” cannot be responsible for the ultrafast decay of KN fluorescence in protic solvents. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Computational study of the mechanism of the photochemical and thermal ring-opening/closure reactions and solvent dependence in spirooxazines

The spirooxazine/merocyanine couple constitutes a photochromic system that can change from the colorless spirooxazine to the intensely colored merocyanine by thermal or photochemical activation by a reaction that opens the spiro ring of the oxazine. The mechanisms of the ring-opening/closure reactions that interconnect these two isomers have been elucidated by means of a computational study. First, we have used the CASSCF/CASPT2 method to determine in detail these mechanisms in the gas phase for a small model that contains the photoactive part of the whole system. We have found that the state of spirooxazine excited by the initial absorption changes gradually to a lower excited state that is involved in a conical intersection that connects it with the ground state of merocyanine. The same conical intersection is involved in the backward photochemical reaction. Second, using a larger model that includes all the heteroatoms of the system and using the DFT (B3LYP) method, we have studied the influence of a solvent environment on the thermal equilibrium between the open and the closed species. It has been observed experimentally that the thermal equilibrium between these forms is practically unaltered by polar aprotic solvents, but it can be displaced toward the colored form in mixtures of polar protic and aprotic solvents, even if the first one is found in a very small proportion. To reproduce the experimental environments, we have taken into account the long-range effect of the polar aprotic solvent considering it a polarizable continuum, as done in the PCM method, and the short-range effect of the protic solvent including some explicit water molecules in the cluster studied at the atomic level. The results obtained are in good agreement with the experimental observations and explain the reason for this peculiar behavior.     

Water solvent effects using continuum and discrete models: The nitromethane molecule,CH3NO2

The first three valence transitions of the two nitromethane conformers (CH₃NO₂) are two dark n → π* transitions and a very intense π → π* transition. In this work, these transitions in gas‐phase and solvated in water of both conformers were investigated theoretically. The polarizable continuum model (PCM), two conductor‐like screening (COSMO) models, and the discrete sequential quantum mechanics/molecular mechanics (S‐QM/MM) method were used to describe the solvation effect on the electronic spectra. Time dependent density functional theory (TDDFT), configuration interaction including all single substitutions and perturbed double excitations (CIS(D)), the symmetry‐adapted‐cluster CI (SAC‐CI), the multistate complete active space second order perturbation theory (CASPT2), and the algebraic‐diagrammatic construction (ADC(2)) electronic structure methods were used. Gas‐phase CASPT2, SAC‐CI, and ADC(2) results are in very good agreement with published experimental and theoretical spectra. Among the continuum models, PCM combined either with CASPT2, SAC‐CI, or B3LYP provided good agreement with available experimental data. COSMO combined with ADC(2) described the overall trends of the transition energy shifts. The effect of increasing the number of explicit water molecules in the S‐QM/MM approach was discussed and the formation of hydrogen bonds was clearly established. By including explicitly 24 water molecules corresponding to the complete first solvation shell in the S‐QM/MM approach, the ADC(2) method gives more accurate results as compared to the TDDFT approach and with similar computational demands. The ADC(2) with S‐QM/MM model is, therefore, the best compromise for accurate solvent calculations in a polar environment. © 2015 Wiley Periodicals, Inc.     

Comparison of polarizable continuum model and quantum mechanics/molecular mechanics solute electronic polarization: study of the optical and magnetic properties of diazines in water

A combination of the polarizable continuum model (PCM) and the hybrid quantum mechanics/molecular mechanics (QM/MM) methodology, PCM-MM/QM, is used to include the solute electronic polarization and then study the solvent effects on the low-lying n→π(?) excitation energy and the (15)N nuclear magnetic shielding of pyrazine and pyridazine in aqueous environment. The results obtained with PCM-MM/QM are compared with two other procedures, i.e., the conventional PCM and the iterative and sequential QM/MM (I-QM/MM). The QM calculations are made using density functional theory in the three procedures. For the excitation energies, the time-dependent B3LYP/6-311+G(d) model is used. For the magnetic shielding, the B3LYP/aug-pcS2(N)/pcS2(C,O,H) is used with the gauge-including atomic orbitals. In both cases, i.e., PCM-MM/QM and I-QM/MM, that use a discrete model of the solvent, the solute is surrounded by a first shell of explicit water molecules embedded by an electrostatic field of point charges for the outer shells. The best results are obtained including 28 explicit water molecules for the spectral calculations and 9 explicit water molecules for the magnetic shielding. Using the PCM-MM/QM methodology the results for the n→π(?) excitation energies of pyridazine and pyrazine are 32,070 ± 80 cm(-1) and 32,675 ± 60 cm(-1), respectively, in good agreement with the corresponding I-MM/QM results of 32,540 ± 80 cm(-1) and 32,710 ± 60 cm(-1) and the experimental results of 33,450-33,580 cm(-1) and 32,700-33,300 cm(-1). For the (15)N magnetic shielding, the corresponding numbers for the gas-water shifts obtained with PCM-MM/QM are 47.4 ± 1.3 ppm for pyridazine and 19.7 ± 1.1 ppm for pyrazine, compared with the I-QM/MM values of 53.4?±?1.3 ppm and 19.5 ± 1.2 ppm and the experimental results of 42-54 ppm and 17-22 ppm, respectively. The agreement between the two procedures is found to be very good and both are in agreement with the experimental values. PCM-MM/QM approach gives a good solute polarization and could be considered in obtaining reliable results within the expected QM/MM accuracy. With this electronic polarization, the solvent effects on the electronic absorption spectra and the (15)N magnetic shielding of the diazines in water are well described by using only an electrostatic approximation. Finally, it is remarked that the experimental and theoretical results suggest that the (15)N nuclear magnetic shielding of any diazine has a clear dependence with the solvent polarity but not directly with the solute-solvent hydrogen bonds.     

Ion-pairing of octyl viologen diiodide in low-polar solvents: an experimental and computational study

We have investigated the ion-pairing and solvent effect on the NMR and UV/vis spectra of 1,1'-di- n-octyl-4,4'-bipyridinium diiodide in various solvents. A strikingly different behavior is observed in the low polar solvent dichloromethane. A large deshielding of the meta bipyridinium core resonance occurs and charge transfer (CT) transitions are observed in the visible region due to the formation of ion-pairs. The CT bands show a marked blue-shift as the polarity of the solvent is increased. Experimental data have been compared with the results of DFT calculations of proton's chemical shifts and TD-DFT calculations of the vertical electronic transitions of model ion-pairs (using the smaller methyl viologen dication) in the gas phase and after the inclusion of the solvent reaction field by means of the PCM scheme. Different geometrical arrangements of the ion-pairs have been investigated, and the direct and indirect solvent effect has been elucidated. A good agreement is obtained which allows one to get insights concerning the CT transitions of this system and the geometry of the ion-pairs in solution of low-polar solvents.     

Solvent effects in the GIAO‐DFT calculations of the 15N NMR chemical shifts of azoles and azines

The calculation of ¹⁵N NMR chemical shifts of 27 azoles and azines in 10 different solvents each has been carried out at the gauge including atomic orbitals density functional theory level in gas phase and applying the integral equation formalism polarizable continuum model (IEF‐PCM) and supermolecule solvation models to account for solvent effects. In the calculation of ¹⁵N NMR, chemical shifts of the nitrogen‐containing heterocycles dissolved in nonpolar and polar aprotic solvents, taking into account solvent effect is sufficient within the IEF‐PCM scheme, whereas for polar protic solvents with large dielectric constants, the use of supermolecule solvation model is recommended. A good agreement between calculated 460 values of ¹⁵N NMR chemical shifts and experiment is found with the IEF‐PCM scheme characterized by MAE of 7.1 ppm in the range of more than 300 ppm (about 2%). The best result is achieved with the supermolecule solvation model performing slightly better (MAE 6.5 ppm). Copyright © 2014 John Wiley & Sons, Ltd.     

Theoretical study of the effects of solvent environment on photophysical properties and electronic structure of paracyclophane chromophores

We use first-principles quantum-chemical approaches to study absorption and emission properties of recently synthesized distyrylbenzene (DSB) derivative chromophores and their dimers (two DSB molecules linked through a [2.2]paracyclophane moiety). Several solvent models are applied to model experimentally observed shifts and radiative lifetimes in Stokes nonpolar organic solvents (toluene) and water. The molecular environment is simulated using the implicit solvation models, as well as explicit water molecules and counterions. Calculations show that neither implicit nor explicit solvent models are sufficient to reproduce experimental observations. The contact pair between the chromophore and counterion, on the other hand, is able to reproduce the experimental data when a partial screening effect of the solvent is taken into account. Based on our simulations we suggest two mechanisms for the excited-state lifetime increase in aqueous solutions. These findings may have a number of implications for organic light-emitting devices, electronic functionalities of soluble polymers and molecular fluorescent labels, and their possible applications as biosensors and charge/energy conduits in nanoassemblies.     

A Theoretical Study of the UV/Visible Absorption and Emission Solvatochromic Properties of Solvent‐Sensitive Dyes

Using the density‐functional vertical self‐consistent reaction field (VSCRF) solvation model, incorporated with the conductor‐like screening model (COSMO) and the self‐consistent reaction field (SCRF) methods, we have studied the solvatochromic shifts of both the absorption and emission bands of four solvent‐sensitive dyes in different solutions. The dye molecules studied here are: S‐TBA merocyanine, Abdel‐Halim's merocyanine, the rigidified aminocoumarin C153, and Nile red. These dyes were selected because they exemplify different structural features likely to impact the solvent‐sensitive fluorescence of “push‐pull”, or merocyanine, fluorophores. All trends of the blue or red shifts were correctly predicted, comparing with the experimental observations. Explicit H‐bonding interactions were also considered in several protic solutions like H₂O, methanol and ethanol, showing that including explicit H‐bonding solvent molecule(s) in the calculations is important to obtain the correct order of the excitation and emission energies. The geometries, electronic structures, dipole moments, and intra‐ and intermolecular charge transfers of the dyes in different solvents are also discussed.     

Thermal and solvent effects on the NMR and UV parameters of some bioreductive drugs

15N NMR chemical shifts and n-->pi* electronic transition energy for metronidazole (1) has been calculated and compared with experimental data. A detailed computational study of 1 is presented, with special attention to the performance of various theoretical methods for reproducing spectroscopic parameters in solution. The most sophisticated approach involves density functional based on the Car-Parrinello molecular dynamics simulations of 1 in aqueous solution (BP86 level) and averaging chemical shifts and deltaE(n-->pi*) over snapshots from the trajectory. In the NMR and UV calculations for these snapshots (performed at the B3LYP level), a small number of discrete water molecules are retained, and the remaining bulk solution effects are included via a polarizable continuum model (PCM). A good agreement with experiment is also obtained using static geometry optimization and NMR computation of pristine 1 employing a PCM approach. Further theoretical predictions are also reported for 17O NMR and deltaE(n-->pi*) of three hydroxycinnamic acid derivatives, which suggest that it is essential to incorporate the dynamics and solvent effects for NMR and UV calculations in the condensed phase.     

Ab initio tools for the accurate prediction of the visible spectra of anthraquinones

The UV/vis absorption spectra of 101 anthraquinones solvated in two protic solvents (methanol and ethanol) has been theoretically predicted using the time-dependent density functional theory (TD-DFT) for the excited state calculations and the polarizable continuum model (PCM) for evaluating bulk solvent effects. Two functionals (B3LYP and PBE0) have been used and they provide similar mean absolute deviations (approximately 0.09 eV) but mean signed errors presenting opposite signs. The errors can be minimized by using simple or multiple linear regression, the latter combining the results of both functionals to reach an optimal estimation of the lambda(max) (mean absolute error 0.06 eV). Specific fittings for the two media have been performed and it turned out that our approach is even more efficient for anthraquinones solvated in ethanol.     

Density functional calculations of electronic g-tensors for semiquinone radical anions. The role of hydrogen bonding and substituent effects

A recently developed density functional approach has been used to carry out a systematic computational study of electronic g-tensors for a series of 1,4-semiquinone radical anions. Good agreement with high-field EPR data in frozen 2-propanol is achieved only after taking into account the significant reduction of g-tensor anisotropy caused by hydrogen bonding to solvent molecules. The comparison of various model systems for the first solvation shell suggests two hydrogen bonds from 2-propanol molecules to each of the carbonyl groups of the radical anions, and one additional hydrogen bond to each of the methoxy groups in ubiquinone systems. 2-Propanol makes stronger hydrogen bonds than water and thus influences g-tensor anisotropy more strongly. Substituent effects at the semiquinone are reproduced quantitatively by the calculations. The g-tensor anisotropy is influenced significantly by the conformations of methyl and methoxy substituents, with opposite contributions. Analyses and interpretations of the interrelations between structure, bonding, and spectroscopic data are provided. The relevance of the computational results for the EPR spectroscopy of semiquinone radical anions in photosynthetic reaction centers is discussed.     

Monte Carlo simulations of the solution structure of simple alcohols in water-acetonitrile mixtures

Monte Carlo simulations have been performed to explore the solution structure of ethyl, isopropyl, isobutyl, and tertiary butyl alcohols in pure water, pure acetonitrile, and different mixtures of the two solvents. The explicit solvent studies in NpT ensembles at T = 298 K illustrate that the solute "discriminates" the solvent's components and that the composition of the first solvation shell differs from that of the bulk solution. Since the polarizable continuum dielectric method (PCM) does not presently model the solvation of molecules with both polar and apolar sites in mixed protic solvents, we suggest a direction for further program development wherein a continuum dielectric method would accept more than one solvent and the solute sites would be solvated by user-defined solvent components. The prevailing solvation model will be determined upon the lowest free energy calculated for a particular solvation pattern of the solute having a specific conformational/tautomeric state. Characterization of equilibrium hydrogen-bond formation becomes a complicated problem that depends on the chemical properties of the solute and its conformation, as well as upon the varying nature of the first solvation shell. For example, while the number of hydrogen bonds to secondary and tertiary alcohol solutes are nearly constant in pure water and in water-acetonitrile mixtures with at least 50% water content, the number of hydrogen bonds to primary alcohols gradually decreases for most of their conformations when acetonitrile content is increased. Nonetheless, the calculations indicate that O-H...O(water) hydrogen bonds are still possible in a small fraction of the arrangements for the solution models with water content of 30% or less. The isopentene solute does not form any observable hydrogen bonds, despite having an electron-rich, double-bond site.     

An explicit quantum chemical method for modeling large solvation shells applied to aminocoumarin C151

The absorption spectra of aminocoumarin C151 in water and n-hexane solution are investigated by an explicit quantum chemical solvent model. We improved the efficiency of the frozen-density embedding scheme, as used in a former study on solvatochromism (J. Chem. Phys. 2005, 122, 094115) to describe very large solvent shells. The computer time used in this new implementation scales approximately linearly (with a low prefactor) with the number of solvent molecules. We test the ability of the frozen-density embedding to describe specific solvent effects due to hydrogen bonding for a small example system, as well as the convergence of the excitation energy with the number of solvent molecules considered in the solvation shell. Calculations with up to 500 water molecules (1500 atoms) in the solvent system are carried out. The absorption spectra are studied for C151 in aqueous or n-hexane solution for direct comparison with experimental data. To obtain snapshots of the dye molecule in solution, for which subsequent excitation energies are calculated, we use a classical molecular dynamics (MD) simulation with a force field adapted to first-principles calculations. In the calculation of solvatochromic shifts between solvents of different polarity, the vertical excitation energy obtained at the equilibrium structure of the isolated chromophore is sometimes taken as a guess for the excitation energy in a nonpolar solvent. Our results show that this is, in general, not an appropriate assumption. This is mainly due to the fact that the solute dynamics is neglected. The experimental shift between n-hexane and water as solvents is qualitatively reproduced, even by the simplest embedding approximation, and the results can be improved by a partial polarization of the frozen density. It is shown that the shift is mainly due to the electronic effect of the water molecules, and the structural effects are similar in n-hexane and water. By including water molecules, which might be directly involved in the excitation, in the embedded region, an agreement with experimental values within 0.05 eV is achieved.     

Solvent effect on the singlet excited-state lifetimes of nucleic acid bases: A computational study of 5-fluorouracil and uracil in acetonitrile and water

The first comprehensive quantum mechanical study of solvent effects on the behavior of the two lowest energy excited states of uracil derivatives is presented. The absorption and emission spectra of uracil and 5-fluorouracil in acetonitrile and aqueous solution have been computed at the time-dependent density-functional theory level, using the polarizable continuum model (PCM) to take into account bulk solvent effects. The computed spectra and the solvent shifts provided by our method are close to their experimental counterpart. The S0/S1 conical intersection, located in the presence of hydrogen-bonded solvent molecules by CASSCF (8/8) calculations, indicates that the mechanism of ground-state recovery, involving out-of-plane motion of the 5 substituent, does not depend on the nature of the solvent. Extensive explorations of the excited-state surfaces in the Franck-Condon (FC) region show that solvent can modulate the accessibility of an additional decay channel, involving a dark n/pi* excited state. This finding provides the first unifying explanation for the experimental trend of 5-fluorouracil excited-state lifetime in different solvents. The microscopic mechanisms underlying solvent effects on the excited-state behavior of nucleobases are discussed.     

Solute-Solvent Interactions in Solutions of Solvatochromic Phenoxides: A Dynamics Simulation Study

Solute-solvent interactions in protic (water, methanol and 2-propanol) and aprotic (DMSO) solvents of four solvatochromic phenoxides, the 4- and 2-pyridiniophenoxides, Brooker’s merocyanine and the N-methyloxyquinolinium betaine, were investigated with the aid of molecular dynamics simulations. Although the size of the first solvation shell of the phenoxide oxygen of all betaines remains constant in the three protic solvents, it comprises increasingly fewer solvent molecules as the volume of the hydroxylic solvent increases. In DMSO, the donor phenoxide group of the 4-pyridiniophenoxide betaine is loosely solvated, leading to an internal charge-transfer with smaller transition energies than in protic media.     

Rare tautomer hypothesis supported by theoretical studies: ab initio investigations of prototropic tautomerism in the N-methyl-p base

Density functional theory calculations were applied to the prediction of the tautomeric properties of N-methyl-P (6-methyl-3,4-dihydro-8H-pyrimido[4,5-c][1,2]oxazin-7-one), a base of the nucleoside analogue dP (6-(2-deoxy-beta-D-ribofuranosyl)-3,4-dihydro-8H-pyrimido[4,5-c][1,2]oxazin-7-one), for which water-solution experimental data have become available recently. The calculations have been performed for three tautomers in the gas phase, with various numbers of water molecules, and within the polarizable continuum model (PCM) of solvation. The obtained results correctly predict the presence of two tautomers and reproduce accurately the experimentally obtained ratio of the two most stable tautomeric forms when using a combination of explicit water molecules and the PCM of solvation. This lends additional support to the rare tautomer hypothesis of substitution mutagenesis in DNA replication.