Adiabatic Ionization Potentials Research Articles

Theoretical characterisation and design of D–π–A star-shaped molecules with triphenylamine as core and diketopyrrolopyrroles as arms for organic solar cells

ABSTRACTA series of novel D–π–A star-shaped molecules with triphenylamine (TPA) fragments as cores, diketopyrrolopyrrole (DPP) fragments as arms, and different conjugate π-bridges those connect TPA and DPP fragments have been designed for small molecules based organic solar cells (OSCs) applications. The optical, electronic, and charge transporting properties have been systematically investigated by means of density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The parameters such as energetic driving force ΔEL-L, adiabatic ionisation potentials (AIP), and adiabatic electron affinities (AEA) were also calculated at the same level to preliminarily evaluate the performance of the OSCs. The results of frontier molecular orbitals (FMOs) show that the designed molecules provide the best match matched energy levels with typical acceptors PCBM, bisPCBM, and PC70BM except for molecule containing benzo[c][1,2,5]thiadiazole unit because of its low energetic driving force ΔEL-L. It turned out that the FMO energy levels, the band gaps, AIP, AEA, and absorption spectrum can be tuned effectively by the introduction of different groups. Additionally, our results suggest that the designed molecules can act as promising candidates for donor materials and ambipolar charge transport materials for OSCs.

Symmetry lowering by cage doping in spherical superatoms: Evaluation of electronic and optical properties of 18‐electron W@Au12Ptn (n = 0‐4) superatomic clusters from relativistic DFT calculations

AbstractAttempts to expand the versatility of well defined clusters are a relevant issue in the design of building blocks for functional nanostructures. Here, we investigate the plausible formation of related structures from the emblematic highly symmetrical 18‐e [W@Au12] cluster. The calculated [W@Au12Ptn] series, with n = 0, 1, 2, 3, and 4, show cohesion energies, HOMO‐LUMO gap, adiabatic electron affinities (AEAs) and adiabatic ionization potentials (AIPs), indicating a relative stability to the parent cluster [W@Au12] experimentally characterized, where clusters with n = 1 and n = 4 are suggested as the most stable with respect to oxidation. The resulting symmetry lowering away from the high icosahedral symmetry upon adding Pt atoms induces a sizable splitting of the frontiers shells, which in turn effectively modify the properties of the calculated clusters, as observed from calculated optical properties. The estimated absorption spectra show an interesting broadening effect of the absorption peaks, which appears as a useful approach for further design of broad black absorbers, which are able to absorb light in a wider range, with potential capabilities to enhance the efficiency of thin film solar cells and photocatalysis processes, among other applications.

Analysis of the S1 ← S0 and D0 ← S1 spectra in m-bromofluorobenzene via resonance-enhanced multiphoton ionization and slow electron velocity-map imaging spectroscopy

Vibrations of m-bromofluorobenzene (m-BrFPh) in the first excited state (S1) and the cationic ground state (D0) are investigated by resonance-enhanced multiphoton ionization (REMPI) spectroscopy and slow electron velocity-map imaging (SEVI) spectroscopy, respectively. Quantum chemical calculations have been adopted to assign the observed vibrational bands, as well. The band origin of the S1 ← S0 electronic transition defines the adiabatic excitation energy to be 36,987 ± 4 cm−1 based on the resonance-enhanced one-color two-photon ionization spectrum of m-BrFPh. And adiabatic ionization potential (IP) of 73,903 ± 8 cm−1 is determined from band origin in the SEVI spectra. Meanwhile, the computed frequencies are in excellent agreement with the experimental observations and Franck-Condon simulations are performed to aid us to confidently assign major vibrational modes in S1 and D0 states. And the changes in the wavenumber of the vibrational modes upon S1 ← S0 and D0 ← S1 transitions are examined. Furthermore, the mixing of vibrational modes both between S0 & S1 and between S1 & D0 has been discussed.

Density functional study of ternary AuxAgyCuz and AuxAgyCuz+ clusters (x + y+z = 5, 6)

ABSTRACTWe report a theoretical investigation of neutral AuxAgyCuz and cationic AuxAgyCuz+ ternary clusters, for x + y+z = 5 and 6. Our study is performed within density functional theory at the TPSSTPSS/SDD level. The geometries, chemical order, binding energy, mixing energy, second difference in the energy, adiabatic ionisation potential of these clusters are evaluated as a function of the whole concentration range. The most probable dissociation channels and the corresponding dissociation energies for the most stable clusters are also determined and discussed.

Substitution effects on 1,3-disubstituted imidazol-2-ylidenes and 1,3-diarylimidazol-2-ylidenes revisited: a theoretical study at DFT level

Effect of substituents on philicity and stability of 1,3-disubstituted imidazol-2-ylidenes and 1,3-diarylimidazol-2-ylidenes was assessed using the following calculations: adiabatic electron affinity and adiabatic ionization potential, global electrophilicity and differential orbital energy scales for philicity, and ΔES–T, ΔEHyd, ΔEiso, and ΔEH–L for stability, with the aid of density functional theory and the results were then compared with each other. In the case of 1,3-disubstituted imidazol-2-ylidene, the carbene with CH3 group has the highest nucleophilic character considering all the above scales and the highest thermodynamic stability. 1,3-Diarylimidazol-2-ylidenes with CH3O and NH2 groups have high-nucleophilic properties and high-stability; their ΔEiso values are also greater than 377 kJ/mol which means that they may be reasonable synthetic targets. While, the presence of electron donating groups at 1,3-disubstituted imidazol-2-ylidene results in ΔEiso > 377 kJ/mol. Nucleophilicity of 1,3-diarylimidazol-2-ylidenes is, to some extent, greater than that of 1,3-disubstituted imidazol-2-ylidenes.

Oxidizing Metal Oxides with Polynuclear Superhalogen: An ab Initio Study.

The ability of metal oxides (CoO, CuO, MgO, MnO2, NiO, SiO2, TiO2, and ZnO) to form stable systems with polynuclear superhalogen (i.e., Mg3F7) is examined on the basis of theoretical considerations supported by ab initio calculations. It is demonstrated that the MeO n ( n = 1, 2) molecules (such as CoO, CuO, MgO, MnO2, NiO, TiO2, ZnO) should form stable and strongly bound (MeO n)+(superhalogen)- salts when combined with the Mg3F7 superhalogen radical (acting as an oxidizing agent). This conclusion is supported by providing: (i) structural deformation of superhalogen upon ionization, (ii) predicted charge flow between each MeO n and superhalogen (which allows estimating the amount of electron density withdrawn from MeO n molecule during the ionization process), (iii) the localization of the spin density distribution, and (iv) the interaction energies and vertical ionization potentials (VIPs) for the compounds obtained at the CCSD(T)/6-311+G(d) level of theory. On the other hand, the Mg3F7 superhalogen was found to be incapable of ionizing molecules whose adiabatic ionization potentials (AIPs) exceed 12 eV (e.g., SiO2). I believe that the results provided in this contribution may likely be of prospective relevance in the future studies on the issue of binding and preventing metal oxide nanoparticles aggregation in the environment before they occur harmful to human health and environment.

Optical properties of bilayer quantum dot models based on coronene and its BN analogues with a BODIPY dye: Theoretical TD-CAM-B3LYP-D3 investigation.

Quantum dots (QD) belong to a class of materials considered technologically important for their tunable absorption and emission properties and a huge application potential in optoelectronic technologies. To date, only simplified monolayer models of QDs and their dimers have been considered when modeling their absorption and/or emission spectra and effects of edge functionalization. Here, we analyze the optical properties of new type electron donor-acceptor bilayer quantum dot models based on coronene and its boron-nitride analogues (electron donors) with a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene dye (Bdp, an electron acceptor) dye by using time-dependent density functional theory. To understand the nature of transition shifts in electronic spectra, we use BN models with strong modification of the HOMO and LUMO: m-BNC (middle hexagonal ring CC bonds are substituted by BN), p-BNC (all peripheral CC bonds are substituted by BN), and f-BNC (all C atoms are replaced by B and N in an alternate manner). Adiabatic ionization potentials of all coronenes were also calculated. The obtained results show that significant interlayer charge transfer (CT) on excitation of bilayer QDs in S1, S2, and S3 states from strong electron donors, coronene (6.93 eV) and m-BNC (6.52 eV), to Bdp will occur. As a result, one can observe only very weak absorption of CT-character in the low-energy spectrum region as well as strong fluorescence quenching of Bdp. On the contrary, for the weak electron donors, p-BNC (7.22 eV) and f-BNC (8.22 eV), strong Bdp-like absorption and fluorescence bands of local excitation character in the low-energy region are expected. Correlation of optical properties of bilayer QDs with ionization potentials of coronene monolayers has been founded. The obtained results can be useful for future graphene-based optoelectronic applications.

A Frank-Kasper polyhedral structure of 17-atom vanadium clusters

A distorted Frank-Kasper polyhedral structure (A) as the putative global minimum was identified for the neutral and charged V17 clusters by using the Monte Carlo basin-hopping algorithm based on semi-empirical Gupta potential and density functional theory calculations. The cationic V17+ cluster reproduces well the experimental infrared multiple photon dissociation spectroscopy, and the calculated adiabatic ionization potentials and electron affinities of the A structure are close to its experimental values. It is also found that the shell-closed V17+ structure can be stabilized by 20 delocalized 3c-2e and 4 delocalized 6c-2e σ bonds on the outer shell and 12 delocalized 4c-2e σ bonds on the inner shell. Our results will inevitably stimulate future theoretical and experimental studies for the design and exploration of largely nanoscale materials.

UV Photoionization of Sodium-Doped Formic Acid Clusters.

The processes involved in the photoionization of sodium-doped clusters are complex, not fully understood for many systems and still strongly debated, especially because of the discrepancy between experimental results and predicted cluster structures. We have performed a study on sodium doped formic acid clusters based on UV photoionization spectroscopy and DFT/TDDFT calculations. Apart from the monomer, all the predicted structures show vertical ionization potential values higher than those obtained by the photoionization measurements. We have calculated the absorption spectra and found many Rydberg-like states near the adiabatic ionization potentials and, crucially, in the UV range where the clusters appearance energies fall. This finding supports the hypothesis of adiabatic contributions in the measured ionization potentials for these clusters.

Analysis of the ionization potentials of small superalkali lithium clusters based on quantum Monte Carlo simulations

In order to investigate the electronic correlation effects in the ionization potentials of small lithium clusters, we obtain accurate ground-state energies using the diffusion quantum Monte Carlo simulation. We decompose both the adiabatic and vertical ionization potentials of the clusters into physical components to analyze the nature of the superalkali characteristics of the lithium clusters. We find that the electron-correlation contribution to the ionization potential is mostly canceled out by the orbital relaxation with net contribution less than 0.5 eV. The superalkali characteristics of the clusters is basically determined by the electrostatic and exchange interactions.

A theoretical study of the adiabatic and vertical ionization potentials of water.

Theoretical predictions of the three lowest adiabatic and vertical ionization potentials of water were obtained from the Feller-Peterson-Dixon approach. This approach combines multiple levels of coupled cluster theory with basis sets as large as aug-cc-pV8Z in some cases and various corrections up to and including full configuration interaction theory. While agreement with experiment for the adiabatic ionization potential of the lowest energy 2B1 state was excellent, differences for other states were much larger, sometimes exceeding 10 kcal/mol (0.43 eV). Errors of this magnitude are inconsistent with previous benchmark work on 52 adiabatic ionization potentials, where a root mean square of 0.20 kcal/mol (0.009 eV) was found. Difficulties in direct comparisons between theory and experiment for vertical ionization potentials are discussed. With regard to the differences found for the 2A1/2Πu and 2B2 adiabatic ionization potentials, a reinterpretation of the experimental spectrum appears justified.

Electrochemical Stability of Closo-Carborane Anions and Their Impact on Cathode Interfacial Properties

Electrochemically stable, charge delocalized anions are essential electrolyte constituents for rechargeable, high voltage magnesium batteries. Within this class of anions, magnesium closo-carborane salts were demonstrated to support reversible magnesium electrodeposition/dissolution in tetraethylene glycol dimethyl ether (tetraglyme, G4) highlighting their cathodic stability.1,2 The corresponding anodic stability of these anions remains undetermined due to the lower anodic stability of the glyme solvents preferred for increased salt solubility, ionic conductivity, and stability against magnesium metal. In this paper, we explore the anodic stability of the carba-closo-dodecaborate anion (CB11H12 -) and select functionalized derivatives thereof relative to the more typical battery electrolyte anions bis(trifluoromethylsulfonyl)imide (TFSI) and tetrafluoroborate (BF4). In solvents of higher anodic stability than the glymes, including 3-methylsulfolane and 1,1,3,3-hexafluoroisopropanol, we demonstrate an oxidation potential of 4.5 V vs. Mg/Mg(II) for the base CB11H12 - anion, which is surprisingly lower than that measured for TFSI or BF4. Computational screening of the adiabatic ionization potential and electron affinity of RCB11H11 - (where R is a functional group that replaces the H-C proton) indicates that substitution of the proton at the carbon vertex with an electron withdrawing group can yield a several hundred millivolt increase in oxidative stability without decreasing the cathodic stability. Synthesis and electrochemical evaluation of the fluoro-carba-closo-dodecaborate validates this prediction and offers a rational design strategy for improved electrolyte stability. Oxidation of either the parent or substituted carba-closo-dodecaborate anion is irreversible, resulting in a neutral radical that incorporates within a surface film. The surface film formed inhibits further electron transfer leading to a varying degree of passivation toward further electrolyte decomposition depending on the solvent employed. The composition and structure of this metastable interface and its Mg cation transport properties will be discussed. O. Tutusaus, R. Mohtadi, T.S. Arthur, F. Mizuno, E.G. Nelson, Y.V. Sevryugina, “An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries,” Angew. Chem. Int. Ed. 2015, 54, 7900.S.G. McArthur, R. Jay, L. Geng, J. Guo, V. Lavallo, “Below the 12-vertex: 10-vertex carborane anions as non-corrosive, halide free, electrolytes for rechargeable Mg batteries,” Chem. Comm. 2017, 53, 4453.

First principles study of structural, electronic and magnetic properties of SnGen(0, ±1) (n = 1–17) clusters

The structures, relative stability and magnetic properties of pure Gen+1, neutral cationic and anionic SnGen (n = 1–17) clusters have been investigated by using the first principles density functional theory implemented in SIESTA packages. We find that with the increasing of cluster size, the Gen+1 and SnGen(0, ±1) clusters tend to adopt compact structures. It has been also found that the Sn atom occupied a peripheral position for SnGen clusters when n < 12 and occupied a core position for n > 12. The structural and electronic properties such as optimized geometries, fragmentation energy, binding energy per atom, HOMO–LUMO gaps and second-order differences in energy of the pure Ge n+1 and SnGen clusters in their ground state are calculated and analyzed. All isomers of neutral SnGen clusters are generally nonmagnetic except for n = 1 and 4, where the total spin magnetic moments is 2μb. The total (DOS) and partial density of states of these clusters have been calculated to understand the origin of peculiar magnetic properties. The cluster size dependence of vertical ionization potentials, vertical electronic affinities, chemical hardness, adiabatic electron affinities and adiabatic ionization potentials have been calculated and discussed.

Structure, fragmentation patterns, and electronic properties of small indium oxide clusters

A theoretical study of nanoparticles of indium oxide, one of the most relevant transparent conducting materials, is reported. By means of Density Functional Theory in the generalized gradient approximation, we investigated the atomic and electronic structures of the neutral and charged indium oxide clusters $$\text{In}_n\text{O}_m^{0/\pm }$$ with n = 1–6 and m = 1–8, as well as related properties like adiabatic ionization potentials and electron affinities. Based on total energy differences between the obtained global minimum configurations of parent clusters and possible fragments, we explored the respective fragmentation channels for cationic clusters and compared our results with those recently observed in Photodissociation measurements (Knight et al. in IJMS 304:29, 2011). The overall good agreement between theory and experiment provides compelling evidence of the calculated properties of these systems, whose knowledge is essential to take advantage of the nanoscale in future technological applications of these materials.

The optical properties of adenine cation in different oligonucleotides: a PCM/TD-DFT study

The absorption spectra of several systems containing an adenine (A) cation are computed in water by TD-DFT calculations, using three different functionals and including solvent effects by a mixed discrete–continuum approach. Our calculations well reproduce the experimental absorption spectrum of deoxyadenosine nucleoside cation (dA+), which provides an intense peak at 350 nm and a weaker one at 600 nm, allowing its assignment. M052X and CAM-B3LYP predict that the hole is essentially localized on a single A base also in the cationic forms of dApdA dinucleotide, both in single and in double strand, and of (dApdT) duplex, exhibiting absorption spectra similar to that of dA+. For all these compounds, B3LYP predicts instead the delocalization of the hole over two A bases. On this ground, it is possible to propose which would be the spectral signature of partial hole delocalization. Vertical and adiabatic ionization potentials for the compounds under investigation are also computed, providing values in good agreement with the available experimental results.

Theoretical analysis of tautomerization of succinimide and analogous compounds: insights from DFT approach

Tautomerizations of biologically and medicinally important heterocyclic compound, 2,5-pyrrolidinedione, commonly known as succinimide and two of its analogous compounds, 2,4-pyrrolidinedione and 3,4-pyrrolidinedione have been investigated at the density functional theory (DFT)/M06-2X level in aqueous medium, implementing polarizable continuum model (PCM). We have extended our investigation of tautomerism to the sulfur analogues of the aforementioned compounds also, i.e., 2,5-pyrrolidinedithione, 2,4-pyrrolidinedithione, and 3,4-pyrrolidinedithione. Tautomerism observed in these compounds are mainly keto-enol, thio-thiol and amine-imine, but we have detected two new kind of tautomerization shown by some of the abovementioned compounds, named as keto-epoxy (for the oxygen analogue) and thio-thioepoxy (for the sulfur analogue) which have not yet been reported in the literature. Relative energies (Er) and activation energies (Ea) have been calculated for all the tautomers and tautomerization processes. The potential energy surfaces (PESs) have been constructed using the M06-2X energy values. It has been observed that the energy difference found in the tautomers of sulfur analogues is relatively lower than that of the corresponding oxygen analogues, so does the activation energy barrier. As one-electron redox properties play an important role in biological systems, we have also explored the effect of conformational changes on the overall redox properties of the said compounds by calculating the adiabatic and vertical ionization potentials (AIPs and VIPs, respectively) and adiabatic electron affinities (AEAs).

IcMRCI+Q study on spectroscopic properties and predissociation mechanisms of electronic states of BF+ cation

In this paper, we study the spectroscopic properties and predissociation mechanisms of 14 states, which come from the first two dissociation channels of the BF+ cation. The potential energy curves of 14 Λ-S (X2Σ+, 12Π, 22Π, 22Σ+, 14Σ+, 14Δ, 14Σ1, 12Δ, 12Σ1, 32Σ+, 14Π, 24Π, 24Σ+, and 32Π) and corresponding 30 Ω states are calculated using the complete active space self-consistent field method, which is followed by the valence internally contracted multireference configuration interaction approach with the Davidson modification. To improve the reliability and accuracy of the potential energy curves, the core-valence correlation and scalar relativistic corrections, as well as the extrapolation of potential energy to the complete basis set limit are taken into account. The spin-orbit coupling is computed using the state interaction approach with the Breit-Pauli Hamiltonian. Based on these potential energy curves, the spectroscopic parameters and vibrational levels are determined for all the bound and quasi-bound Λ-S and Ω states. The present ground-state spectroscopic constants match well with the available experimental data. In addition, the vertical and adiabatic ionization potentials from the X1Σ+ state of BF molecule to the X2Σ+, 12Π, and 22Σ+ states of BF+ cation are calculated. The results of BF+(X2Σ+) ← BF(X1Σ+) ionization are in good agreement with the measurements. Various curve crossings of Λ-S states are revealed. We calculate the spin-orbit matrix elements between two interacting electronic states in the curve crossing region. With the help of present spin-orbit coupling matrix elements, we analyze the predissociation mechanisms of X2Σ+ and 32Π states along with the perturbations of the nearby states to 22Π, 14Σ+ and 32Σ+ states for the first time. The predissociation of X2Σ+ and 32Π states have a chance to occur around the vibrational levels υ"=30 and υ'=0 due to spin-orbit coupling, respectively. The present results also indicate that the υ' ≥ 9 vibrational levels of 22Π state are perturbed by the crossing states 22Σ+, 14Σ+, 14Δ, 14Σ1, 12Δ, 12Σ1, 32Σ+, and 14Π, that the υ' ≥ 4 vibrational levels of 14Σ+ state are perturbed via the interacting states 14Σ1 and 12Σ1, and the great perturbations between υ' ≥ 4 vibrational levels of 32Σ+ state and υ' ≥ 0 vibrational levels of 14Π state. For the 30 Ω state, we also calculate the relative energies of dissociation limits compared with the lowest one matching well with the experimental ones. Finally, the Franck-Condon factors, Einstein coefficients, and radiative lifetimes are evaluated for the 22Π (υ'=0-9)-X2Σ+, 22Σ+ (υ'=0-2)-X2Σ+, (3)1/2-(1)1/21st well, and (2)3/2 (υ'=0-9)-(1)1/21st well transitions.

Density functional theory of InCn+(n=110) clusters

Small indium-doped carbon clusters InCn+(n=110) are systematically studied by the density functional theory at the B3 LYP/LANL2 DZ level. The computed properties include equilibrium geometries, electronic energies, vibrational frequencies, dipole moments and rotational constants for individual species. The calculation results show that the open-chain linear isomers with the indium atom bound to the end of the carbon chain are the most stable geometry in all cases. There must exist a cyclic or fan structure in the metastable or the third stable structure of cluster. The bigger the size of the cluster, the more obvious the stability of the structure is. The electronic ground state is found to be alternately a triplet for even n and a singlet for odd n with the only exception of InC+. It is generally observed that the spin contamination is not serious for all electronic ground states because the s2 values are uniform and in general deviate slightly from the pure spin values, and the B3 LYP wave functions are nearly spin-pure. It is also found that in the lowest-energy linear structure, the InC bond is longer (from 2.319 to 2.850 ) than the corresponding CC bonds in a range from 1.268 to 1.360 . The CC distances can be assimilated to moderately strong double bonds underlying a clear bonding in the corresponding structures. In addition, we observe a clear alternation in CC distances. The CoddCeven distances are shorter than the CevenCodd ones which mainly results from the charge distribution and spin density. According to the calculation and analysis of the incremental binding energy and the second difference we can deduce an even-odd alternation in the cluster stability for the linear InCn+, with their n-odd members being more stable than the adjacent even-numbered ones. This parity effect also appears in the adiabatic ionization potential curves. The analysis of magnetic properties shows the even-odd alternation with n-even clusters presenting higher values of magnetic moment than n-odd ones. The study of the polarizability indicates that the average values of both the polarization tensors and the anisotropic invariants increase with the size of cluster increasing.

The predictive power of aromaticity: quantitative correlation between aromaticity and ionization potentials and HOMO-LUMO gaps in oligomers of benzene, pyrrole, furan, and thiophene.

Aromaticity is a central and ubiquitous concept in organic chemistry, and is used extensively to explain various phenomena. Yet, aromaticity cannot be observed or measured as a property in its own right and, to date, only qualitative and semi-quantitative relationships have been described between aromaticity and an observable property. We now demonstrate for the first time a robust quantitative relationship between the HOMO-LUMO gap and adiabatic ionization potential of a polycyclic aromatic hydrocarbon oligomer - both measurable physical quantities - and its aromaticity, as quantified by the Nucleus Independent Chemical Shift (NICS) index. The agreement found for a range of structurally and electronically diverse oligomeric systems of varying lengths is so well-behaved as to enable accurate prediction of the properties of longer members of the respective oligomer family. The established correlation allows for preliminary screening of compounds geared towards functional use.

The bridged effect on the geometric, optoelectronic and charge transfer properties of the triphenylamine–bithiophene-based dyes: a DFT study

The dye-sensitized solar cells containing a triphenylamine unit as the electron donor connected with a terminal cyanoacrylic acid electron acceptor by 2,2′-bithiophene as π-bridged (D-π-A) has been investigated by density functional theory (DFT) at the B3LYP/6-31G(d) level to shed light on the bridged effect on geometric and electronic properties of the designed dyes. Also, time-dependent DFT (TD-DFT) at a TD-BH and H/6-31+G(d)//BH and H/6-31G(d) level of theory was selected to modulate the electronic absorption spectra and charge-transfer properties of studied dyes. The calculated results show that the strong electron-withdrawing groups bridged the 2,2′-bithiophene efficiently, reduce the energy gaps and provide a red shift of the absorption spectra. The calculated absorption spectra in tetrahydrofuran (THF) are in good agreement with available experimental value for dye D1. Generally, the fundamental parameters, such as vertical and adiabatic ionization potentials (IPa/IPv), vertical and adiabatic electron affinities (EAa/EAv), electron extraction potentials and hole extraction potentials, including hole/electron reorganization energies (λ +/λ −), of studied dyes have been discussed. The improved electronic coupling constant ( $$\left| {V_{\text{RP}} } \right|$$ ), electron injection force ( $$\Delta G^{\text{inject}}$$ ) and light-harvesting efficiency of dye D5 revealed that this dye can be used as a potential sensitizer for TiO2 nanocrystalline solar cells.