Charge-transfer Electronic States Research Articles

Photo-oxidation of methanol in complexes with pyrido[2,3-b]pyrazine: a nonadiabatic molecular dynamics study.

Excited-state Proton-Coupled Electron Transfer (PCET) constitutes a key step in the photo-oxidation of small, electron-rich systems possessing acidic hydrogen atoms, such as water or alcohols, which can play a vital role in green hydrogen production. In this contribution, we employ ab initio quantum-chemical methods and on-the-fly nonadiabatic molecular dynamics simulations to study the mechanism and the photodynamics of PCET in 1 : 1 pyrido[2,3-b]pyrazine complexes with methanol. We find the process to be ultrafast and efficient when the intramolecular hydrogen bond is formed with one of the β-positioned nitrogen atoms. The complex exhibiting a hydrogen bond with an isolated nitrogen site, on the contrary, shows much lower reactivity. We explain this effect with the stabilization of the reactive ππ* charge-transfer electronic state in the former case.

Voltage tuning of photoinduced charge transfer resonances between 2,2′-bipyridine and a nanostructured silver electrode

The effect of applied electric potentials and excitation wavelengths (785, 532, 473 nm) on the Surface-Enhanced Raman scattering (SERS) of 2,2′-bipyridine (2,2′-bpy) adsorbed on a silver electrode has been analyzed on the basis of a charge transfer (CT) resonance mechanism. DFT/TD-DFT calculations performed for a simple model of surface complex (Ag2-2,2′-bpy) point out that 2,2′-bpy preferably adsorbs through both nitrogen atoms in a cis-conformation with edge-on orientation. The calculated spectra in resonance with the two first bright metal-to-molecule charge transfer electronic states (CT0;B1 and CT1;B1) account for the main experimental features: the selective enhancement of the totally symmetric modes recorded at about 1585, 1560 and 1480 cm−1 under 532 nm line, staying the 1560 cm−1 band as the most intense under 473 nm line at more negative electrode potential. The split of SERS bands recorded in the 1600, 1000 and 600 cm−1 regions point to the existence of a monodentate coordination of the cis-conformer. The calculated resonance condition up to CT0 and CT1 states is fulfilled under 532 and 488 nm excitation lines, respectively, agreeing with the behaviour of the intensity-potential profile of the bands for each excitation wavelength.

Exciton Dissociation in a Model Organic Interface: Excitonic State-Based Surface Hopping versus Multiconfigurational Time-Dependent Hartree.

Quantum dynamical simulations are essential for a molecular-level understanding of light-induced processes in optoelectronic materials, but they tend to be computationally demanding. We introduce an efficient mixed quantum-classical nonadiabatic molecular dynamics method termed eXcitonic state-based Surface Hopping (X-SH), which propagates the electronic Schrödinger equation in the space of local excitonic and charge-transfer electronic states, coupled to the thermal motion of the nuclear degrees of freedom. The method is applied to exciton decay in a 1D model of a fullerene–oligothiophene junction, and the results are compared to the ones from a fully quantum dynamical treatment at the level of the Multilayer Multiconfigurational Time-Dependent Hartree (ML-MCTDH) approach. Both methods predict that charge-separated states are formed on the 10–100 fs time scale via multiple “hot-exciton dissociation” pathways. The results demonstrate that X-SH is a promising tool advancing the simulation of photoexcited processes from the molecular to the true nanomaterials scale.

Charge-transfer electronic states in organic solar cells: a TDDFT study.

The prediction of new organic photovoltaic materials in organic solar cells (OSCs) must include a precise description of charge-transfer states because they are involved in electron-transfer processes such as charge separation and charge recombination which govern the device efficiency. Also, as the experimental performance of an optoelectronic device is measured for nonequilibrium nanostructures, computational approaches need models that can incorporate morphology effects. Usually, this aspect is treated by molecular dynamics simulation (MDS) methodologies; however, methodologies and formalisms to calculate the electron-transfer processes are still controversial and sometimes do not connect their information with the phase morphologies. In this work we propose a simple and fast characterization of electron-transfer processes to find the rate constants by analysing the distribution of vertical excitation energies of both local excitation (LE) and charge-transfer (CT) states using TD-DFT calculations in the donor-acceptor pair structures which were extracted from MDS. This proposal assumes that conformational changes are prevented and equilibria are not achieved while the electron-transfer events take effect, and thus the only pathway that connects the LE and CT states is their surface crossing point where an ideal distribution might exist. Different density functionals and dialectric models were tested. The results indicate a close relationship between the proposal and experimental data for electron-transfer events, suggesting the application of this method in the rational design of new photovoltaic materials.

Organic Solar Cells Based on Non-fullerene Small-Molecule Acceptors: Impact of Substituent Position

Summary Molecular engineering of non-fullerene small-molecule acceptors (SMAs) plays a key role in enhancing the performance of organic solar cells. An effective strategy is to introduce functional groups into SMA end groups to tune the electronic and morphological properties of polymer/SMA blends. Here, molecular dynamics simulations and long-range corrected density functional theory calculations are combined to examine the impact of the position of methoxy substitution in the SMA end groups. As representative systems, blends of the IT-OM small-molecule acceptor with the PBDB-T polymer donor are explored; three different positions of the methoxy substitution of the IT-OM end groups are examined. By considering intermolecular mixing and packing, the energetic distribution of the charge-transfer electronic states, the exciton-dissociation and non-radiative recombination processes, and the electron-transfer rates among adjacent acceptors, we provide a comprehensive molecular-scale rationalization of the significant experimental variations in device performance for PBDB-T/IT-OM-based solar cells as a function of methoxy position.

Organic Solar Cells Based on Non-Fullerene Small-Molecule Acceptors: Impact of Substituent Position

Molecular engineering of non-fullerene small-molecule acceptors (SMAs) plays a key role in enhancing the performance of organic solar cells. An effective strategy is to introduce functional groups into SMA end-groups to tune the electronic and morphological properties of polymer/SMA blends. Here, molecular dynamics simulations and long-range corrected density functional theory calculations are combined to examine the impact of the position of methoxy substitution in the SMA end-groups. As representative systems, blends of the IT-OM small-molecule acceptor with the PBDB-T polymer donor are explored; three different positions of the methoxy substitution of the IT-OM end-groups are examined. By considering intermolecular mixing and packing, the energetic distribution of the charge-transfer electronic states, the exciton dissociation and nonradiative recombination processes, and the electron-transfer rates among adjacent acceptors, we provide a comprehensive molecular-scale rationalization of the significant experimental variations in device performance for PBDB-T/IT-OM-based solar cells as a function of methoxy position.

Charge-transfer electronic states in organic solar cells

In organic solar cells, the charge-transfer (CT) electronic states that form at the interface between the electron-donor (D) and electron-acceptor (A) materials have a crucial role in exciton-dissociation, charge-separation and charge-recombination processes. Since the introduction of active layers consisting of D–A bulk heterojunctions, CT states have been the focus of extensive experimental and theoretical studies. In this Review, we assess the current understanding of CT states and describe how factors such as the geometry of the D–A interface, electronic polarization and the extent of electron delocalization affect their nature and influence the radiative and non-radiative decay processes. We focus on the description and application of fundamental concepts, which provides the framework to discuss the path to organic solar cells with efficiencies comparable to those in inorganic photovoltaic technologies. The charge-transfer electronic states that form at the interfaces between electron-donor and electron-acceptor components have a key role in the electronic processes in organic solar cells. This Review describes the current understanding of how these charge-transfer states affect device performance.

Assessing the nature of the charge-transfer electronic states in organic solar cells

The charge-transfer electronic states appearing at the donor-acceptor interfaces in organic solar cells mediate exciton dissociation, charge generation, and charge recombination. To date, the characterization of their nature has been carried out on the basis of models that only involve the charge-transfer state and the ground state. Here, we demonstrate that it is essential to go beyond such a two-state model and to consider explicitly as well the electronic and vibrational couplings with the local absorbing state on the donor and/or acceptor. We have thus developed a three-state vibronic model that allows us: to provide a reliable description of the optical absorption features related to the charge-transfer states; to underline the erroneous interpretations stemming from the application of the semi-classical two-state model; and to rationalize how the hybridization between the local-excitation state and charge-transfer state can lead to lower non-radiative voltage losses and higher power conversion efficiencies.

Bulk Heterojunction Solar Cells: Impact of Minor Structural Modifications to the Polymer Backbone on the Polymer–Fullerene Mixing and Packing and on the Fullerene–Fullerene Connecting Network

AbstractThe morphology of the active layer of a bulk heterojunction solar cell, made of a blend of an electron‐donating polymer and an electron‐accepting fullerene derivative, is known to play a determining role in device performance. Here, a combination of molecular dynamics simulations and long‐range corrected density functional theory calculations is used to elucidate the molecular‐scale effects that even minor structural changes to the polymer backbone can have on the “local” morphology; this study focuses on the extent of polymer–fullerene mixing, on their packing, and on the characteristics of the fullerene–fullerene connecting network in the mixed regions, aspects that are difficult to access experimentally. Three representative polymer donors are investigated: (i) poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′″‐diyl)] (PffBT4T‐2OD); (ii) poly[(2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′″‐diyl)] (PBT4T‐2OD), where the fluorine atoms in the benzothiadiazole moieties of PffBT4T‐2OD are replaced with hydrogen atoms; and (iii) poly[(2,2′‐bithiophene)‐alt‐(4,7‐bis((2‐decyltetradecyl)thiophen‐2‐yl)‐5,6‐difluoro‐2‐propyl‐2H‐benzo[d][1,2,3]triazole)] (PT2‐FTAZ), where the sulfur atoms in the benzothiadiazole moieties of PffBT4T‐2OD are replaced with nitrogen atoms carrying a linear C3H7 side‐chain; these polymers are mixed with the phenyl‐C71‐butyric acid methyl ester (PC71BM) acceptor. This study also discusses the nature of the charge‐transfer electronic states appearing at the donor–acceptor interfaces, the electronic couplings relevant for the charge‐recombination process, and the electron‐transfer features between neighboring PC71BM molecules.

Time-evolution study of photoinduced charge-transfer in tertiary amine-fluorophore systems

Photoinduced charge transfer in a fluorescent sensor of organophosphorus nerve agents is examined by solution of the time dependent Schrödinger equation, under the influence of an external electromagnetic field and employing potential energy curves obtained by density functional theory (DFT) and time dependent DFT (TDDFT) calculations for the ground and the excited states, respectively. The systems of interest here consist of a tertiary amine-pyrene molecule, with different numbers of CH2 spacer units between the t-amine and the pyrene. Quenching of pyrene emission has been observed in these systems, to different extent depending on the number of spacer units, which is due to photoinduced electron transfer from the t-amine to pyrene. Here, we present a new approach based on time-evolution for the explanation of the experimental observation of the quenching of pyrene emission. In this work the inversion coordinate at nitrogen is considered as a generalized coordinate for the charge-transfer process. Vibrational levels, dipole moments and dipole transition moments of the ground, excited, and charge transfer electronic states along the inversion coordinate are computed by DFT and TDDFT calculations. The time evolution of the excitation probability between the vibrational levels of the ground state and the first excited state and the charge transfer state has been calculated for different excitation frequencies. The results are in agreement with experimental observations regarding the photoinduced electron transfer and decreasing probability for charge transfer with increasing number of CH2 spacer units between the t-amine and the pyrene.

Spectroscopy of charge transfer states in Mg1 – x Ni x O

Photoluminescence and photoluminescence excitation spectra of solid solution Mg1–x Ni x O (x = 0.008) have been analyzed. The contributions of charge transfer electronic states and nonradiative Auger relaxation to the formation of the photoluminescence spectrum are discussed.

Design and Synthesis of Charge-Transfer-Based Conjugated Polyelectrolytes as Multicolor Light-Up Probes

Cationic poly[9,9-bis(6′-N,N,N-trimethylammonium)hexyl)fluorene-alt-4,7-(2,1,3-benzothiadiazole) dibromide] (PFBT) and poly[9,9-bis(6′-(N,N,N-trimethylammonium)hexyl)fluorenyldivinylene-alt-4,7-(2,1,3-benzothiadiazole) dibromide] (PFVBT) are designed and synthesized to serve as multicolor light-up probes for biomolecular quantification. Because of the charge-transfer electronic states of the polymers, they exhibit weak fluorescence in aqueous media which can be significantly enhanced by increasing the hydrophobicity of polymeric microenvironment. Molecular orbital simulations further reveal that the presence of vinyl bonds endows PFVBT with a stronger charge-transfer character relative to that of PFBT. Both PFBT and PFVBT exhibit linear fluorescence enhancement as a function of bovine serum albumin (BSA) or DNA concentration in buffer solution, allowing effective biomolecular quantification. Of particular interest is that the light-up responses of PFBT or PFVBT in the presence of BSA and DNA are different...

Localized Charge Transfer in CsAu·NH3: 1H and 133Cs Nuclear Magnetic Resonance

We report results from 1H and 133Cs nuclear magnetic resonance (NMR) studies on CsAu·NH3. This compound has recently been synthesized and belongs to the family of ammoniates. The intense blue color of the material, which is not observed in the parent compounds, suggests that a charge-transfer electronic state is formed. The 1H NMR line shape and relaxation rates are found to be very similar to the corresponding properties in pure ammonia. However, the 133Cs-NMR properties of CsAu·NH3 strongly deviate from the corresponding ones in CsAu, and we show that the former can be interpreted consistently within a localized charge distribution due to either an anharmonic charge density wave state induced by a charge transfer process or an Anderson localization mechanism.

Molecular structure and optosensing behavior of di-2-pyridyl ketone benzoylhydrazone in non-aqueous solvents

Crystals of di-2-pyridyl ketone benzoylhydrazone (dpkbh) obtained from a dimethylsulfoxide (DMSO) solution of dpkbh are in the monoclinic space group, P21/c. Structural analysis reveals anti-parallel, non-planar, one-dimensional tapes of dpkbh with a network of intra- and intermolecular hydrogen bonds. Optical measurements on dpkbh in polar non-aqueous solvents revealed the presence of interlocked low-(α-) and high-(β-) energy intraligand charge-transfer electronic states may be due to dpk π–π∗ followed by dpk to benzoyl charge-transfer. The equilibrium distribution of the low-(α-) and high-(β-) energy electronic states is solvent dependent, controlled by the hydrogen bonding capacity of surrounding solvent molecules. The interplay between the α- and β-conformations of dpkbh allowed calculations of their extinction coefficients by forcing the equilibrium to shift to one conformation using chemical stimuli. In N,N-dimethylformamide (DMF), extinction coefficients of 45,000±2000 and 15,000±2000M−1cm−1 were calculated for the α- and β-conformations of dpkbh at λmax, respectively, when excess acid was added to a DMF solution of dpkbh. The weak bond energies of the hydrogen bonds, the reversibility and the sensitivity of the high- and low-energy electronic states to their surroundings in polar non-aqueous solvents allow for the use of this system as molecular sensor for a variety of stimuli that include metal ions, acids and bases. Metal ions in concentrations <10−7M can be detected and determined using this system (dpkbh and surrounding solvent molecules).

Raman scattering and X-ray diffraction study in layered cuprates

Raman scattering and powder X-ray diffraction in the parent compounds of T,T'-phase and (Ca 0.86Sr 0.14)CuO 2 were measured to examine the two-magnon (ω 2m) and highest phonon energy (ω 2p) dependences on Cu-O bond length ( d), and to determine the structural parameters of the T'-phase. We found that both ω 2m and ω 2p exhibit strong power-law dependence on d, ω 2m∝ d -4.6, and ω 2p∝ d -6.3, in the T'-phase except for Gd 2CuO 4, and both energies for Gd 2CuO 4 deviate from the power-law relation. The strong d dependence of ω 2p suggests that this phonon is strongly coupled with charge-transfer electronic state. The observed phonon is assigned to two-phonon scattering of the bond-stretching mode of Cu and O atoms in the basal plane. The depression of ω 2p for Gd 2CuO 4 implies a structural change, such as oxygen distortion in the CuO 2 plane, which influences the charge-transfer energy gap Δ and ω 2m. The Δ values were estimated from the Madelung site potentials V i , which were calculated based on the crystal structural parameters determined by Rietveld analysis. Cu 3d-O 2p transfer energy t pd, and on-site Coulomb repulsive potentials, U d and U p, were determined using a one-dimensional Cu 2O cluster model by fitting ω 2m as a function of d. Finally, we discuss the relationship between crystal structure and carrier doping. The result of ΔV: ( V R - V Cu ) dependence on d suggests that the carrier concentration is not constant in T'-phase and change in the carrier concentration influences T c in these materials.

Radiative decay of the Ar 2+2 excimer: an ab initio study

The radiative decay of bound excited charge-transfer electronic states of Ar 2+ 2 is studied via ab initio effective operator QDPT calculations of potential energy and transition dipole moment curves. The assignment of the ‘third continuum“ in the emission spectrum of the Ar plasma to bound-repulsive transitions of Ar 2+ 2 is supported.