Resonance Raman spectra and excited state properties of methyl viologen and its radical cation from time-dependent density functional theory.

Time-dependent density functional theory (TDDFT) was applied to gain insights into the electronic and vibrational spectroscopic properties of an important electron transport mediator, methyl viologen (MV2+ ). An organic dication, MV2+ has numerous applications in electrochemistry that include energy conversion and storage, environmental remediation, and chemical sensing and electrosynthesis. MV2+ is easily reduced by a single electron transfer to form a radical cation species (MV•+ ), which has an intense UV-visible absorption near 600 nm. The redox properties of the MV2+ /MV•+ couple and light-sensitivity of MV•+ have made the system appealing for photo-electrochemical energy conversion (e.g., solar hydrogen generation from water) and the study of photo-induced charge transfer processes through electronic absorption and resonance Raman spectroscopic measurements. The reported work applies leading TDDFT approaches to investigate the electronic and vibrational spectroscopic properties of MV2+ and MV•+ . Using a conventional hybrid exchange functional (B3-LYP) and a long-range corrected hybrid exchange functional (ωB97X-D3), including with a conductor-like polarizable continuum model to account for solvation, the electronic absorption and resonance Raman spectra predicted are in good agreement with experiment. Also analyzed are the charge transfer character and natural transition orbitals derived from the TDDFT vertical excitations calculated. The findings and models developed further the understanding of the electronic properties of viologens and related organic redox mediators important in renewable energy applications and serve as a reference for guiding the interpretation of electronic absorption and Raman spectra of the ions.

A comprehensive analysis of charge transfer effects on donor-pyrene (bridge)-acceptor systems using different substituents.

The alternant polycyclic aromatic hydrocarbon pyrene has photophysical properties that can be tuned with different donor and acceptor substituents. Recently, a D (donor)-Pyrene (bridge)-A (acceptor) system, DPA, with the electron donor N,N-dimethylaniline (DMA), and the electron acceptor trifluoromethylphenyl (TFM), was investigated by means of time-resolved spectroscopic measurements (J. Phys. Chem. Lett. 2021, 12, 2226-2231). DPA shows great promise for potential applications in organic electronic devices. In this work, we used the ab initio second-order algebraic diagrammatic construction method ADC(2) to investigate the excited-state properties of a series of analogous DPA systems, including the originally synthesized DPAs. The additionally investigated substituents were amino, fluorine, and methoxy as donors and nitrile and nitro groups as acceptors. The focus of this work was on characterizing the lowest excited singlet states regarding charge transfer (CT) and local excitation (LE) characters. For the DMA-pyrene-TFM system, the ADC(2) calculations show two initial electronic states relevant for interpreting the photodynamics. The bright S1 state is locally excited within the pyrene moiety, and an S2 state is localized ~0.5 eV above S1 and characterized as a donor to pyrene CT state. HOMO and LUMO energies were employed to assess the efficiency of the DPA compounds for organic photovoltaics (OPVs). HOMO-LUMO and optical gaps were used to estimate power conversion and light-harvesting efficiencies for practical applications in organic solar cells. Considering the systems using smaller D/A substituents, compounds with the strong acceptor NO2 substituent group show enhanced CT and promising properties for use in OPVs. Some of the other compounds with small substituents are also found to be competitive in this regard.

Informing air-carbon ablation modeling with theoretical calculations of atomic oxygen and nitrogen interacting with carbon surfaces.

To understand the gas-surface chemistry above the thermal protection system of a hypersonic vehicle, it is necessary to map out the kinetics of key elementary reaction steps. In this work, extensive periodic density functional theory (DFT) calculations are performed to elucidate the interaction of atomic oxygen and nitrogen with both the basal plane and edge sites of highly oriented pyrolytic graphite (HOPG). Reaction energies and barriers are determined for adsorption, desorption, diffusion, recombination, and several reactions. These DFT results are compared with the most recent finite-rate model for air-carbon ablation. Our DFT results corroborated some of the parameters used in the model but suggest that further refinement may be necessary for others. The calculations reported here will help to establish a predictive kinetic model for the complex reaction network present under hypersonic flight conditions.

Polyradical character assessment using multireference calculations and comparison with density-functional derived fractional occupation number weighted density analysis.

The biradicaloid character of different types of polycyclic aromatic hydrocarbons (PAHs) based on small band gaps is an important descriptor to assess their opto-electronic properties. In this work, the unpaired electron densities and numbers of unpaired electrons (NU values) calculated at the high-level multireference averaged quadratic coupled-cluster (MR-AQCC) method are used to develop a test set to assess the capabilities of different biradical descriptors based on density functional theory. A benchmark collection of 29 different compounds has been selected. The DFT descriptors contain primarily the fractional occupation number weighted electron density (FOD) based on simplified thermally-assisted-occupation density functional theory (TAO-DFT) calculations, but the singlet-triplet energy difference and other descriptors denoted as y0 and nLUNO have been considered as well. After adjustment of the literature-recommended finite temperatures, a very good, detailed agreement between unpaired density and FOD analysis is observed which is also manifested in excellent statistical correlations. The other two descriptors also show good correlations even though the absolute scaling is not satisfactory. A new linear fit of FOD data to the MR-AQCC reference values leads to an improved regression relation for determining the recommended finite temperature value in dependence of the Hartree-Fock exchange. This provides the basis for fast and reliable assessment of the biradical character of many classes of PAHs without the need for performing computationally extended MR calculations.

Quantum Dynamical Investigation of Dihydrogen-Hydride Exchange in a Transition-Metal Polyhydride Complex.

The ongoing shift toward clean, sustainable energy is a primary driving force behind hydrogen fuel research. Safe and effective storage of hydrogen is a major challenge (particularly for mobile applications) and requires a detailed understanding of the atomic level interactions of hydrogen with its host materials. The light mass of hydrogen, however, implies that quantum effects are important, so a quantum dynamical treatment is required to properly account for these effects in computational simulations. As one such example, we describe herein the hydrogen exchange dynamics between a hydride and a dihydrogen ligand in the [FeH(H2)(PH3)4]+ model complex. A global three-dimensional (3D) potential energy surface (PES) was constructed by fitting to and interpolating from a discrete set of grid points computed using density functional theory; exact quantum dynamical calculations were then carried out on the 3D PES using discrete variable representation basis sets. Energy levels and their quantum tunneling splittings were computed up to 3000 cm-1 above the ground state. Within that energy range, all three fundamentals have been identified using wave function plots, as well as the first three overtones of the exchange (reaction coordinate) motion and several of its combination bands. From the tunneling splittings, the Boltzmann-averaged tunneling rates were computed. The Arrhenius plot of the total exchange rate shows a clear transition around 150 K, below which the activation energy is essentially zero and above which it is less than half of the electronic structure barrier. This indicates that exchange rates are governed by quantum tunneling throughout the relevant temperature range with the low-temperature regime dominated by a single quantum (ground) state. This work is the first-ever fully quantum dynamical study to investigate the hydrogen exchange dynamics between hydride and dihydrogen ligands coordinated to a transition-metal complex.

High-Level Multireference Investigations on the Electronic States in Single-Vacancy (SV) Graphene Defects Using a Pyrene-SV Model.

The nonplanar character of graphene with a single carbon vacancy (SV) defect is investigated utilizing a pyrene-SV model system by way of complete-active-space self-consistent field theory (CASSCF) and multireference configuration interaction singles and doubles (MR-CISD) calculations. Planar structures were optimized with both methods, showing the 3B1 state to be the ground state with three energetically close states within an energy range of 1 eV. These planar structures constitute saddle points. However, following the out-of-plane imaginary frequency yields more stable (by 0.22 to 0.53 eV) but nonplanar structures of Cs symmetry. Of these, the 1A' structure is the lowest in energy and is strongly deformed into an L shape. Following a further out-of-plane imaginary frequency in the nonplanar structures leads to the most stable but most deformed singlet structure of C1 symmetry. In this structure, a bond is formed between the carbon atom with the dangling bond and a carbon of the cyclopentadienyl ring. This bond stabilizes the structure by more than 3 eV compared to the planar 3B1 structure. Higher excited states were calculated at the MR-CISD level, showing a grouping of four states low in energy and higher states starting around 3 eV.

Exploration of Graphene Defect Reactivity toward a Hydrogen Radical Utilizing a Preactivated Circumcoronene Model.

A preexisting chemisorbed defect is well-known to increase the reactivity of graphene which is normally chemically inert. Specifically, the presence of chemisorbed hydrogen atoms forming an sp3-hybridized C-H bond is known to increase the reactivity of neighboring carbon atoms toward additional hydrogenation with wide-ranging applications from materials science to astrochemistry. In this work, static DFT and DFT-based direct dynamics simulations are used to characterize the reactivity of a graphene sheet around an existing C-H bond defect. The spin density landscape shows how to guide subsequent H atom additions, always bonding most strongly to the carbon atom with greatest spin density. Molecular dynamics of an impinging H atom under thermal conditions with defect graphene was used to determine the statistics of probable reactions. The most frequent outcome is inelastic scattering (48%) and then Eley-Rideal (ER) abstraction of the chemisorbed H atom as vibrationally hot H2 (40%), while the least likely, but probably most interesting, result is formation of a novel C-H bond (12%). The C-H bonds always form in the ß sublattice. The carbon atom in the para position shows to be most reactive toward the incoming H atom, followed by the ortho carbon, in agreement with the spin density computed in the static calculations. Globally, the graphene energy surface is repulsive, but the defects create local channels into this energy surface through which reactants can move locally through and react with the activated surface without a barrier.

A General New Method for Calculating the Molecular Nonpolar Surface for Analysis of LC-MS Data.

The accurate determination of the nonpolar surface area of glycans is vital when utilizing liquid chromatograph/mass spectrometry (LC-MS) for structural characterization. A new approach for defining and computing nonpolar surface areas based on continuum solvation models (CS-NPSA) is presented. It is based on the classification of individual surface elements representing the solvent accessible surface used for the description of the polarized charge density elements in the CS models. Each element can be classified as polar or nonpolar according to a threshold value. The summation of the nonpolar elements then results in the NPSA resulting in a very fine resolution of this surface. The further advantage of the CS-NPSA approach is the straightforward connection to standard quantum chemical methods and program packages. The method has been analyzed in terms of the contributions of different atoms to the NPSA. The analysis showed that not only atoms normally classified as nonpolar contributed to the NPSA, but at least partially also atoms next to polar atoms or N atoms. By virtue of the construction of the solvent accessible surface, atoms in the inner regions of a molecule can be automatically identified as not contributing to the NPSA. The method has been applied to a variety of examples such as the phenylbutanehydrazide series, model dextrans consisting of glucose units and biantennary glycans. Linear correlation of the CS-NPSA values with retention times obtained from liquid chromatographic separations measurements in the mentioned cases give excellent results and promise for more extended applications on a larger variety of compounds.

Insights into adsorption, diffusion, and reactions of atomic nitrogen on a highly oriented pyrolytic graphite surface.

To gain insight into the nitrogen-related gas-surface reaction dynamics on carbon-based thermal protection systems of hypersonic vehicles, we have investigated the adsorption, diffusion, and reactions of atomic nitrogen, N(4S), on the (0001) face of graphite using periodic density functional theory with a dispersion corrected functional. The atomic nitrogen is found to bind with pristine graphite at a bridge site, with a barrier of 0.88 eV for diffusing to an adjacent bridge site. Its adsorption energy at defect sites is significantly higher, while that between graphene layers is lower. The formation of N2 via Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms was also investigated. In the LH pathway, the recombinative desorption of N2 proceeds via a transition state with a relatively low barrier (0.53 eV). In addition, there is a metastable surface species, which is capable of trapping the nascent N2 at low surface temperatures as a result of the large energy disposal into the N-N vibration. The desorbed N2 is highly excited in both of its translational and vibrational degrees of freedom. The ER reaction is direct and fast, and it also leads to translationally and internally excited N2. Finally, the formation of CN from a defect site is calculated to be endoergic by 2.75 eV. These results are used to rationalize the results of recent molecular beam experiments.

Reaction mechanism for fluorination reactions with hydroxylated alumina sites: Pathways promoting aluminum combustion.

Density functional theory calculations were used to reveal the mechanism for the fluorination reaction of active Lewis acid sites on alumina structures, which is important in understanding the pyrophoric processes involving Al particles. In this reaction, hydroxyl groups of active sites are replaced by fluorine anions. Alumina structures were represented by three aluminum aqua hydroxo clusters (labeled AlOOH), in which the Al atom had different coordination spheres, particularly four, five, or six. The F-bearing molecules HF, CH3F, and CF4 were taken as reactants for the fluorination reactions. The overall reaction was represented by four reaction steps as follows: (i) formation of the reaction complex, (ii) activation of the transition state (TS), (iii) deactivation of the TS with a formation of the product complex, and (iv) its decomplexation to individual products. The active reaction center of the TS structure is four-membered, in which two bonds break heterolytically and two form. The lowest reaction barriers were observed for the HF molecule, while the two other molecules had significantly higher reaction barriers. Similarly, the largest overall reaction energies (in absolute value) were found for HF, especially for the five- and six-coordinated Al centers. While the positive charge on the Al center remained almost constant throughout the reaction steps, large charge changes were observed for carbon bearing molecules with a formation of the carbenium cations in the TS step. Realizing the important role of HF in promoting exothermic reactions will enable new molecular design strategies for transforming energy release properties of aluminum powder fuels.

Interplay of Biradicaloid Character and Singlet/Triplet Energy Splitting for cis-/trans-Diindenoacenes and Related Benzothiophene-Capped Oligomers as Revealed by Extended Multireference Calculations.

The biradicaloid character of different types of polycyclic aromatic hydrocarbons is an important quality that guides the development of new materials with interesting magneto-optical properties. Diindenoacene-based systems represent such a class of promising compounds. In this work, the three types trans-diindenoacenes, cis-diindenoacenes, and trans-dicyclopentaacenobis(benzothiophenes) have been studied by means of advanced ab initio methods. The descriptors singlet/triplet splitting energy (ΔES-T), effective number of unpaired electrons (NU), unpaired electron density, and the harmonic oscillator measure of aromaticity have been used to characterize the biradicaloid properties of these species. For all trans structures, low-spin singlet ground states were found, in agreement with previous investigations. Increasing the length of the inner acene chain decreased the ΔES-T and strongly increased the NU values of the singlet state. The cis-diindenoacenes displayed a greatly increased biradicaloid character, indicating enhanced chemical instability. The thiophene rings in the trans-dicyclopentaacenobis(benzothiophenes) structures were found to simultaneously restrict the unpaired electron density from extending into the terminal six-membered rings and confine the unpaired electron density found in the core benzene rings.

Benchmark ab initio calculations on intermolecular structures and the exciton character of poly(p-phenylenevinylene) dimers.

Benchmark ab initio calculations have been performed for poly(p-phenylenevinylene) (PPV) dimers, a paradigmatic material for studying excitation energy transfer mechanisms. Second-order Møller-Plesset perturbation theory was utilized with the scaled opposite spin approach (SOS-MP2) and correlation consistent basis sets to determine the geometric properties and interaction energies in the ground state. Vertical excitations and optimized structures for the S1 state were computed using the SOS second-order algebraic diagrammatic construction method. For the ground state properties, extrapolation to the complete basis set (CBS) limit and correction for the basis set superposition error (BSSE) were performed. While all results computed with different basis sets and considering BSSE correction or not agreed at the CBS limit, a strong bias was observed either using augmented basis sets or BSSE corrections, proving that these approaches are not advisable for calculating intermolecular distances and interaction energies with smaller basis sets. The lower states for vertical excitations were largely local excitons where the hole/electron pair was confined to single chains. For higher excited states, interchain charge transfer (CT) states were also observed. Geometry optimization of the S1 state led to significant reductions in the intermolecular distances and energetic stabilization, with Stokes shifts between 1.4 eV and 0.9 eV (with increasing chain length), and significant CT values between 0.5e and 0.4e.

Exploring reactivity and product formation in N(4S) collisions with pristine and defected graphene with direct dynamics simulations.

Atomic nitrogen is formed in the high-temperature shock layer of hypersonic vehicles and contributes to the ablation of their thermal protection systems (TPSs). To gain atomic-level understanding of the ablation of carbon-based TPS, collisions of hyperthermal atomic nitrogen on representative carbon surfaces have recently be investigated using molecular beams. In this work, we report direct dynamics simulations of atomic-nitrogen [N(4S)] collisions with pristine, defected, and oxidized graphene. Apart from non-reactive scattering of nitrogen atoms, various forms of nitridation of graphene were observed in our simulations. Furthermore, a number of gaseous molecules, including the experimentally observed CN molecule, have been found to desorb as a result of N-atom bombardment. These results provide a foundation for understanding the molecular beam experiment and for modeling the ablation of carbon-based TPSs and for future improvement of their properties.

The generality of the GUGA MRCI approach in COLUMBUS for treating complex quantum chemistry.

The core part of the program system COLUMBUS allows highly efficient calculations using variational multireference (MR) methods in the framework of configuration interaction with single and double excitations (MR-CISD) and averaged quadratic coupled-cluster calculations (MR-AQCC), based on uncontracted sets of configurations and the graphical unitary group approach (GUGA). The availability of analytic MR-CISD and MR-AQCC energy gradients and analytic nonadiabatic couplings for MR-CISD enables exciting applications including, e.g., investigations of π-conjugated biradicaloid compounds, calculations of multitudes of excited states, development of diabatization procedures, and furnishing the electronic structure information for on-the-fly surface nonadiabatic dynamics. With fully variational uncontracted spin-orbit MRCI, COLUMBUS provides a unique possibility of performing high-level calculations on compounds containing heavy atoms up to lanthanides and actinides. Crucial for carrying out all of these calculations effectively is the availability of an efficient parallel code for the CI step. Configuration spaces of several billion in size now can be treated quite routinely on standard parallel computer clusters. Emerging developments in COLUMBUS, including the all configuration mean energy multiconfiguration self-consistent field method and the graphically contracted function method, promise to allow practically unlimited configuration space dimensions. Spin density based on the GUGA approach, analytic spin-orbit energy gradients, possibilities for local electron correlation MR calculations, development of general interfaces for nonadiabatic dynamics, and MRCI linear vibronic coupling models conclude this overview.

Diradical Organic One-Dimensional Polymers Synthesized on a Metallic Surface.

We report on the synthesis and characterization of atomically precise one-dimensional diradical peripentacene polymers on a Au(111) surface. By means of high-resolution scanning probe microscopy complemented by theoretical simulations, we provide evidence of their magnetic properties, which arise from the presence of two unpaired spins at their termini. Additionally, we probe a transition of their magnetic properties related to the length of the polymer. Peripentacene dimers exhibit an antiferromagnetic (S=0) singlet ground state. They are characterized by singlet-triplet spin-flip inelastic excitations with an effective exchange coupling (Jeff ) of 2.5 meV, whereas trimers and longer peripentacene polymers reveal a paramagnetic nature and feature Kondo fingerprints at each terminus due to the unpaired spin. Our work provides access to the precise fabrication of polymers featuring diradical character which are potentially useful in carbon-based optoelectronics and spintronics.

A Multireference Ab Initio Study of the Diradical Isomers of Pyrazine.

Three diradical pyrazine isomers were characterized using highly correlated, multireference methods. The lowest lying singlet and triplet state geometries of 2,3-didehydropyrazine ( ortho), 2,5-didehydropyrazine ( para), and 2,6-didehydropyrazine ( meta) were determined. Two active reference spaces were utilized. The complete active space (CAS) (8,8) includes the σ and σ* orbitals on the dehydrocarbon atoms as well as the valence π and π* orbitals. The CAS (12,10) reference space includes two additional orbitals corresponding to the in-phase and out-of-phase nitrogen lone pair orbitals. Adiabatic and vertical gaps between the lowest lying singlet and triplet states, optimized geometries, canonicalized orbital energies, unpaired electron densities, and spin polarization effects were compared. We find that the singlet states of each diradical isomer contain two significantly weighted configurations, and the larger active space is necessary for the proper physical characterization of both the singlet and triplet states. The singlet-triplet splitting is very small for the 2,3-didehydropyrazine ( ortho) and 2,6-didehydropyrazine ( meta) isomers (+1.8 and -1.4 kcal/mol, respectively) and significant for the 2,5-didehydropyrazine ( para) isomer (+28.2 kcal/mol). Singlet geometries show through-space interactions between the dehydocarbon atoms in the 2,3-didehydropyrazine ( ortho) and 2,6-didehydropyrazine ( meta) isomers. An analysis of the effectively unpaired electrons suggests that the 2,5-didehydropyrazine ( para) isomer also displays through-bond coupling between the diradical electrons.

Structure and electronic states of a graphene double vacancy with an embedded Si dopant.

Silicon represents a common intrinsic impurity in graphene, bonding to either three or four carbon neighbors, respectively, in a single or double carbon vacancy. We investigate the effect of the latter defect (Si-C4) on the structural and electronic properties of graphene using density functional theory. Calculations based both on molecular models and with periodic boundary conditions have been performed. The two-carbon vacancy was constructed from pyrene (pyrene-2C) which was then expanded to circumpyrene-2C. The structural characterization of these cases revealed that the ground state is slightly non-planar, with the bonding carbons displaced from the plane by up to ±0.2 Å. This non-planar structure was confirmed by embedding the defect into a 10 × 8 supercell of graphene, resulting in 0.22 eV lower energy than the previously considered planar structure. Natural bond orbital analysis showed sp3 hybridization at the silicon atom for the non-planar structure and sp2d hybridization for the planar structure. Atomically resolved electron energy loss spectroscopy and corresponding spectrum simulations provide a mixed picture: a flat structure provides a slightly better overall spectrum match, but a small observed pre-peak is only present in the corrugated simulation. Considering the small energy barrier between the two equivalent corrugated conformations, both structures could plausibly exist as a superposition over the experimental time scale of seconds.

Intermolecular interactions and charge transfer transitions in aromatic hydrocarbon-tetracyanoethylene complexes.

A comprehensive theoretical study of the electronically excited states in complexes between tetracyanoethylene (TCNE) and three aromatic electron donors, benzene, naphthalene and anthracene, was performed with a focus on charge transfer (CT) transitions. The results show that the algebraic diagrammatic construction method to second order (ADC(2)) provides excellent possibilities for reliable calculations of CT states. Significant improvements in the accuracy of the computed transition energies are obtained by using the scaled opposite-spin (SOS) variant of ADC(2). Solvent effects were examined on the basis of the conductor-like screening model (COSMO) which has been implemented recently in the ADC(2) method. The dielectric constant and the refractive index of dichloromethane have been chosen in the COSMO calculations to compare with experimental solvatochromic effects. The computation of optimized ground state geometries and enthalpies of formation has been performed at the second-order Møller-Plesset perturbation theory (MP2) level. By comparison with experimental data and with high-level coupled-cluster methods including explicitly correlated (F12) wave functions, the importance of the SOS approach is demonstrated for the ground state as well. In the benzene-TCNE complex, the two lowest electronic excitations are of CT character whereas in the naphthalene and anthracene TCNE complexes three low-lying CT states are observed. As expected, they are strongly stabilized by the solvent. Geometry optimization in the lowest excited state allowed the calculation of fluorescence transitions. Solvent effects lead to a zero gap between S1 and S0 for the anthracene-TCNE complex. Therefore, in the series of benzene-TCNE to anthracene a change from a radiative to a nonradiative decay mechanism to the ground state is to be expected.

The effect of water on gold supported chiral graphene nanoribbons: rupture of conjugation by an alternating hydrogenation pattern.

In the last few years we have observed a breakpoint in the development of graphene-derived technologies, such as liquid phase filtering and their application to electronics. In most of these cases, they imply exposure of the material to solvents and ambient moisture, either in the fabrication of the material or the final device. The present study demonstrates the sensitivity of graphene nanoribbon (GNR) zigzag edges to water, even in extremely low concentrations. We have addressed the unique reactivity of (3,1)-chiral GNR with moisture on Au(111). Water shows a reductive behaviour, hydrogenating the central carbon of the zigzag segments. By combining scanning tunnelling microscopy (STM) with simulations, we demonstrate how their reactivity reaches a thermodynamic limit when half of the unit cells are reduced, resulting in an alternating pattern of hydrogenated and pristine unit cells starting from the terminal segments. Once a quasi-perfect alternation is reached, the reaction stops regardless of the water concentration. The hydrogenated segments limit the electronic conjugation of the GNR, but the reduction can be reversed both by tip manipulation and annealing. Selective tip-induced dehydrogenation allowed the stabilization of radical states at the edges of the ribbons, while the annealing of the sample completely recovered the original, pristine GNR.

Ab initio modeling of excitonic and charge-transfer states in organic semiconductors: the PTB1/PCBM low band gap system.

A detailed quantum chemical simulation of the excitonic and charge-transfer (CT) states of a bulk heterojunction model containing poly(thieno[3,4-b]thiophene benzodithiophene) (PTB1)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is reported. The largest molecular model contains two stacked PTB1 trimer chains interacting with C60 positioned on top of and lateral to the (PTB1)3 stack. The calculations were performed using the algebraic diagrammatic construction method to second order (ADC(2)). One main result of the calculations is that the CT states are located below the bright inter-chain excitonic state, directly accessible via internal conversion processes. The other important aspects of the calculations are the formation of discrete bands of CT states originating from the lateral C60's and the importance of inter-chain charge delocalization for the stability of the CT states. A simple model for the charge separation step is also given, revealing the energetic feasibility of the overall photovoltaic process.