Diabatic States Research Articles

Distance and Orientation Dependence of Triplet-Triplet Energy Transfer Couplings Based on Nonorthogonal Multireference Wave Functions.

Triplet-triplet energy transfer (TEnT) is of particular interest in various photochemical, photobiological, and energy science processes. It involves the exchange of spin and energy of electrons between two molecular fragments. Here, quasi-diabatic self-consistent field solutions were used to obtain the diabatic states involved in TEnT. The resonant Hartree-Fock approach was used to compute the nonorthogonal matrix elements for the two-state or four-state effective Hamiltonian and the overlap matrix. From the symmetric orthogonalized Hamiltonian, electronic coupling elements between the diabatic states in the TEnT process can be obtained. Two structural models, namely, naphthalene dimer and the 2,2'-bifluorene molecule, were employed to investigate the role of distance and orientation of the molecular fragments on the energy transfer process. It is observed that the inclusion of charge transfer states is critical to obtain the correct description of TEnT couplings. We discuss the effectiveness of the two-state model and four-state model in the successful evaluation of TEnT couplings. Spin density plots and biorthogonal orbitals were utilized to verify that the correct diabatic electronic structure of the TEnT states was determined.

Accurate and Efficient Schemes for Mapping Out Two Isolated Seams of Conical Intersections with Neural Networks Solely Based on Adiabatic Energies: A Case Study of H+ + NO(X2Π) → H + NO+(X1Σ+).

A new scheme in the neural network (NN) diabatization approach that solely utilizes the adiabatic energies for constructing the global diabatic potential energy matrices (PEMs) of the molecular systems with two isolated seams of conical intersections (CIs) is proposed. Taking a prototype charge transfer reaction H+ + NO(X2Π) → H + NO+(X1Σ+), where two seams of CIs are located at the different linear geometries N-O-H and O-N-H, for example, the diabatization with the new scheme including a diabatic state constraint is shown to map out the topographies of both two linear CIs with 100% of the success rate in 10 different trainings, while the diabatization without such constraint hardly represents CIs, in which the avoided crossings appear instead. Simultaneously, we propose a scheme to separate the whole reactive space into three different regions and define the minimal Euclidean distances for each region to efficiently sample the energy points for the NN trainings. Through adjusting the minimal Euclidean distances, the number of the adiabatic energy data needed in the construction of diabatic PEM can be heavily decreased, lowered from ∼2000 to ∼280 energy points, which is much less than the number (>22 000) of ab initio energy points used in earlier spline diabatic PEM. Further quantum dynamic calculations show that the reaction probabilities, vibrational state distributions, and vibrational state resolved differential cross sections are well reproduced on the new NN diabatic PEM, validating these schemes for constructing the diabatic PEM.

Extending non-adiabatic rate theory to strong electronic couplings in the Marcus inverted regime

Electron transfer reactions play an essential role in many chemical and biological processes. Fermi’s golden rule (GR), which assumes that the coupling between electronic states is small, has formed the foundation of electron transfer rate theory; however, in short range electron/energy transfer reactions, this coupling can become very large, and, therefore, Fermi’s GR fails to make even qualitatively accurate rate predictions. In this paper, I present a simple modified GR theory to describe electron transfer in the Marcus inverted regime at arbitrarily large electronic coupling strengths. This theory is based on an optimal global rotation of the diabatic states, which makes it compatible with existing methods for calculating GR rates that can account for nuclear quantum effects with anharmonic potentials. Furthermore, the optimal GR (OGR) theory can also be combined with analytic theories for non-adiabatic rates, such as Marcus theory and Marcus–Levich–Jortner theory, offering clear physical insights into strong electronic coupling effects in non-adiabatic processes. OGR theory is also tested on a large set of spin-boson models and an anharmonic model against exact quantum dynamics calculations, where it performs well, correctly predicting rate turnover at large coupling strengths. Finally, an example application to a boron-dipyrromethane–anthracene photosensitizer reveals that strong coupling effects inhibit excited state charge recombination in this system, reducing the rate of this process by a factor of 4. Overall, OGR theory offers a new approach to calculating electron transfer rates at strong couplings, offering new physical insights into a range of non-adiabatic processes.

Differential Shannon Entropies and Mutual Information in a Curve Crossing System: Adiabatic and Diabatic Decompositions.

The differential Shannon entropy provides a measure for the localization of a wave function. We regard the vibrational wave packet motion in a curve crossing system and calculate time-dependent entropies. Using a numerical example, we analyze how localization inside diabatic and adiabatic states can be accessed and discuss the differences between these two representations. In order to do so, we extend the usual entropy definition and introduce novel state-selective entropies. These quantities contain information on the form of the nuclear density components on the one hand and on the state population on the other, and it is shown how the contribution of the population can be removed. Having the state-selective entropies at hand, two additional functions derived from these, namely, the conditional entropy and the mutual information, are determined and compared. We find that these quantities relate closely to correlation effects rooted in different electronic properties of the system.

Compensation States Approach in the Hybrid Diabatization Scheme: Extension to Multidimensional Data and Properties.

The diabatization of reactive systems for more than just a couple of states is a very demanding problem and generally requires advanced diabatization techniques. Especially for dissociative processes, the drastic changes in the adiabatic wave functions often would require large diabatic state bases, which quickly become impractical. Recently, we addressed this problem by the compensation states approach developed in the context of our hybrid diabatization scheme. This scheme utilizes wave function as well as energy data in combination with a diabatic potential model. In regions where the initial diabatic state basis becomes insufficient for an appropriate representation of the adiabatic states, new model states are generated. The new model states compensate for the state space not spanned by the initial diabatic basis. Such a compensation state is obtained by projecting the initial diabatic state space out of the adiabatic wave function. This yields a very efficient basis representation of the electronic Hamiltonian. The present work presents two new aspects. First, it is shown how other operators like the spin-orbit operator in the framework of the Effective Relativistic Coupling by Asymptotic Representation (ERCAR) can be evaluated in this compact model state space without losing the correct wave function information and accuracy. Second, the extension of the approach to multidimensional potential energy surface models is presented for methyl iodide including the C-I dissociation coordinate and the angular H3C-I bending coordinates.

Theoretical investigation of distal charge separation in a perylenediimide trimer

An exciton–phonon (ex–ph) model based on our recently developed block interaction product basis framework is introduced to simulate the distal charge separation (CS) process in aggregated perylenediimide (PDI) trimer incorporating the quantum dynamic method, i.e., the time-dependent density matrix renormalization group. The electronic Hamiltonian in the ex–ph model is represented by nine constructed diabatic states, which include three local excited (LE) states and six charge transfer (CT) states from both the neighboring and distal chromophores. These diabatic states are automatically generated from the direct products of the leading localized neutral or ionic states of each chromophore’s reduced density matrix, which are obtained from ab initio quantum chemical calculation of the subsystem consisting of the targeted chromophore and its nearest neighbors, thus considering the interaction of the adjacent environment. In order to quantum-dynamically simulate the distal CS process with massive coupled vibrational modes in molecular aggregates, we used our recently proposed hierarchical mapping approach to renormalize these modes and truncate those vibrational modes that are not effectively coupled with electronic states accordingly. The simulation result demonstrates that the formation of the distal CS process undergoes an intermediate state of adjacent CT, i.e., starts from the LE states, passes through an adjacent CT state to generate the intermediates (∼200 fs), and then formalizes the targeted distal CS via further charge transference (∼1 ps). This finding agrees well with the results observed in the experiment, indicating that our scheme is capable of quantitatively investigating the CS process in a realistic aggregated PDI trimer and can also be potentially applied to exploring CS and other photoinduced processes in larger systems.

Diabatic Valence-Hole Concept.

A global diabatization scheme, based on the "valence-hole" concept, has been previously applied to model webs of avoided crossings that exist in four electronic-state symmetry manifolds of C2 (1Πg, 3Πg, 1Σu+, and 3Σu+). Here, this model is extended to the electronically excited states of four more molecules: CN (2Σ+), N2 (3Πu), SiC (3Π), and Si2 (3Πg). Many strangenesses in the spectroscopic observations (e.g., energy level structure, predissociation linewidths, and radiative lifetimes) for all four electronic state systems discussed here are accounted for by this unified model. The key concept of the model is valence-hole electron configurations: 3σ24σ11π45σ2 in CN (2Σ+), 2σg22σu11πu43σg21πg1 in N2 (3Πu), 5σ26σ17σ22π3 in SiC (3Π), and 4σg24σu15σg22πu3 in Si2 (3Πg), all of which have a triply occupied "valence-core" (i.e., 2σg22σu1 or the equivalent). These valence-hole configurations have a nominal bond order of three or higher and correlate with high-energy separated-atom limits with an np ← ns (n = 2, 3) promotion in one of the atomic constituents. On its way to dissociation, the strongly bound diabatic valence-hole state crosses multiple weakly bound or repulsive states, which belong to electron configurations with a completely filled valence-core. These curve crossings between diabatic potentials result in a network of many avoided crossings among multiple electronic states, analogous to the well-studied electronic structure landscape of ionic-covalent crossings in strongly ionic molecules. Considering the unique role of valence-hole states in shaping the global electronic structure, the valence-hole concept should be added to our intuitive framework of chemical bonding.

Landau–Zener–Stückelberg–Majorana-like dynamics induced by tunneling of spin qubit states in a multiband two-state magnetic quantum wire

We investigate the transfer between spin quantum bit (qubit) states and study the Landau–Zener–Stückelberg–Majorana (LZSM)-like dynamics of tunneling spin qubits in a multiband two-state magnetic quantum wire. Indeed, within the framework of an optical parabolic potential in a three-dimensional (3D) heterostructure quantum wire and under the influence of an external time-varying magnetic field, a model for a multiband two-state magnetic quantum wire is developed. Here, the external magnetic field is used to coherently manipulate and control spin qubit states. By driving the system through an avoided crossing, we consider the associated effective quantum two-level system (TLS) related to the spin qubit states in each band, driving by an external coherent magnetic field in which the related Hamiltonian is Hermitian, and which generally paves a way to LZSM interferometry. Thus, we establish the analytical expressions of the energy eigenvalues in each band and derive the analytical solution of the dynamical evolution of the tunneling probabilities of the associated TLS. Accordingly, nonadiabatic and adiabatic tunneling probabilities (survival and transition) are calculated for each band of the multiband TLS. In this respect, the nonadiabatic and adiabatic dynamical evolutions of the tunneling probabilities of spin qubit populations in the first four bands, with band quantum numbers n = 0, 1, 2 and 3 are analyzed. As a result, depending on the amplitude strength of the driven magnetic field and the magnitude of the driving frequency, we report two striking nonadiabatic and adiabatic scenarios in each band for both the diabatic and adiabatic states. In this context, driving the two states of each band of the multiband TLS related to the spin qubit states through an avoided level crossing can result in nontrivial and incoherent dynamics at certain phases, resulting to apparent inaccurate probabilities, especially in the case of strong driven magnetic field and high driving frequency.

Hybrid Density Functional Valence Bond Method with Multistate Treatment.

Recently, a hybrid density functional valence bond (VB) method, λ-DFVB(U), has been proposed and shown to give accuracy that is comparable to that of CASPT2 in calculations of atomization energies, atomic excitation energies, and reaction barriers, while its computational cost is approximately the same as the valence bond self-consistent-field (VBSCF) method. However, the interaction between electronic states is not included in λ-DFVB(U) since the last step of λ-DFVB(U) is not a diagonalization of the Hamiltonian matrix on the electronic state basis. Therefore, λ-DFVB(U) gives the wrong topology of the potential energy surfaces (PESs) near the conical intersection region. In the present paper, we propose a novel hybrid density functional VB method with multistate treatment, named λ-DFVB(MS), in which an effective Hamiltonian matrix is constructed on the basis of the diabatic states obtained by the valence-bond-based compression approach for the diabatization scheme, and the interaction between electronic states can be included through the diagonalization of the effective Hamiltonian matrix. Test calculations show that λ-DFVB(MS) gives the correct topology of the PESs near the conical intersection region. We also show that the VBSCF wave function with selected VB structures can be applied as a reference in λ-DFVB(MS).

Optical Absorption Properties in Pentacene/Tetracene Solid Solutions.

Modifying the optical and electronic properties of crystalline organic thin films is of great interest for improving the performance of modern organic semiconductor devices. Therein, the statistical mixing of molecules to form a solid solution provides an opportunity to fine-tune optical and electronic properties. Unfortunately, the diversity of intermolecular interactions renders mixed organic crystals highly complex, and a holistic picture is still lacking. Here, we report a study of the optical absorption properties in solid solutions of pentacene and tetracene, two prototypical organic semiconductors. In the mixtures, the optical properties can be continuously modified by statistical mixing at the molecular level. Comparison with time-dependent density functional theory calculations on occupationally disordered clusters unravels the electronic origin of the low energy optical transitions. The disorder partially relaxes the selection rules, leading to additional optical transitions that manifest as optical broadening. Furthermore, the contribution of diabatic charge-transfer states is modified in the mixtures, reducing the observed splitting in the 0-0 vibronic transition. Additional comparisons with other blended systems generalize our results and indicate that changes in the polarizability of the molecular environment in organic thin-film blends induce shifts in the absorption spectrum.

Investigation of excited states of BODIPY derivatives and non-orthogonal dimers from the perspective of singlet fission.

We report state of the art electronic structure calculations RICC2 and XMCQDPT of BODIPY nonorthogonal dimers to understand the photophysical processes from the intramolecular singlet fission (iSF) perspective. We have calculated singlet, triplet and quintet states at the XMCQDPT(8,8)/cc-pVDZ level of theory and diabatic singlet states at the XMCQDPT(4,4)/cc-pVDZ level of theory. In all the systems studied, charge transfer states (1(CA) and 1(AC)) couple strongly with locally excited (1(S1S0)) and multiexcitonic (1(T1T1)) states. The rates of formation of the multiexcitonic state from the locally excited state are very low on account of large activation energy (E(1(T1T1)) - E(1(S1S0))). A relaxed scan along the torsional angle revealed contrasting results for axial and orthogonal conformers. We proposed a probable mechanism for contrasting photophysical properties of dimers B[3,3] and B[2,8]. We also found that substitution of CN, NH2 and BH2 at meso, β and α positions reduces the energy gap (ΔSF = 2E(T1) - E(S1)) significantly, making iSF a competing process in triplet state generation. Intrigued by the success of the CN group at the meso position in reducing the energy gap, we also studied the azaBODIPY monomer and its derivatives using the same methodology. The iSF is slightly endoergic with ΔSF ∼ 0.2 eV in these systems and iSF may play an important role in their photophysical responses.

Hydrogen-iodine scattering. I. Development of an accurate spin-orbit coupled diabatic potential energy model.

The scattering of H by I is a prototypical model system for light-heavy scattering in which relativistic coupling effects must be taken into account. Scattering calculations depend strongly on the accuracy of the potential energy surface (PES) model. The methodology to obtain such an accurate PES model suitable for scattering calculations is presented, which includes spin-orbit (SO) coupling within the Effective Relativistic Coupling by Asymptotic Representation (ERCAR) approach. In this approach, the SO coupling is determined only for the atomic states of the heavy atom, and the geometry dependence of the SO effect is accounted for by a diabatization with respect to asymptotic states. The accuracy of the full model, composed of a Coulomb part and the SO model, is achieved in the following ways. For the SO model, the extended ERCAR approach is applied, which accounts for both intra-state and inter-state SO coupling, and an extended number of diabatic states are included. The corresponding coupling constants for the SO operator are obtained from experiments, which are more accurate than computed values. In the Coulomb Hamiltonian model, special attention is paid to the long range behavior and accurate c6 dispersion coefficients. The flexibility and accuracy of this Coulomb model are achieved by combining partial models for three different regions. These are merged via artificial neural networks, which also refine the model further. In this way, an extremely accurate PES model for hydrogen iodide is obtained, suitable for accurate scattering calculations.

Efficient analytical gradients of property-based diabatic states: Geometry optimizations for localized holes.

We present efficient analytical gradients of property-based diabatic states and couplings using a Lagrangian formalism. Unlike previous formulations, the method achieves a computational scaling that is independent of the number of adiabatic states used to construct the diabats. The approach is generalizable to other property-based diabatization schemes and electronic structure methods as long as analytical energy gradients are available and integral derivatives with the property operator can be formed. We also introduce a scheme to phase and reorder diabats to ensure their continuity between molecular configurations. We demonstrate this for the specific case of Boys diabatic states obtained from state-averaged complete active space self-consistent field electronic structure calculations with GPU acceleration in the TeraChem package. The method is used to test the Condon approximation for the hole transfer in an explicitly solvated model DNA oligomer.

Finding Excited-State Minimum Energy Crossing Points on a Budget: Non-Self-Consistent Tight-Binding Methods.

The automated exploration and identification of minimum energy conical intersections (MECIs) is a valuable computational strategy for the study of photochemical processes. Due to the immense computational effort involved in calculating non-adiabatic derivative coupling vectors, simplifications have been introduced focusing instead on minimum energy crossing points (MECPs), where promising attempts were made with semiempirical quantum mechanical methods. A simplified treatment for describing crossing points between almost arbitrary diabatic states based on a non-self-consistent extended tight-binding method, GFN0-xTB, is presented. Involving only a single diagonalization of the Hamiltonian, the method can provide energies and gradients for multiple electronic states, which can be used in a derivative coupling-vector-free scheme to calculate MECPs. By comparison with high-lying MECIs of benchmark systems, it is demonstrated that the identified geometries are good starting points for further MECI refinement with ab initio methods.

Dynamical Simulations of Carotenoid Photoexcited States Using Density Matrix Renormalization Group Techniques.

We present a dynamical simulation scheme to model the highly correlated excited state dynamics of linear polyenes. We apply it to investigate the internal conversion processes of carotenoids following their photoexcitation. We use the extended Hubbard-Peierls model, , to describe the π-electronic system coupled to nuclear degrees of freedom. This is supplemented by a Hamiltonian, , that explicitly breaks both the particle-hole and two-fold rotation symmetries of idealized carotenoid structures. The electronic degrees of freedom are treated quantum mechanically by solving the time-dependent Schrödinger equation using the adaptive time-dependent DMRG (tDMRG) method, while nuclear dynamics are treated via the Ehrenfest equations of motion. By defining adiabatic excited states as the eigenstates of the full Hamiltonian, , and diabatic excited states as eigenstates of , we present a computational framework to monitor the internal conversion process from the initial photoexcited 11Bu+ state to the singlet triplet-pair states of carotenoids. We further incorporate Lanczos-DMRG to the tDMRG-Ehrenfest method to calculate transient absorption spectra from the evolving photoexcited state. We describe in detail the accuracy and convergence criteria for DMRG, and show that this method accurately describes the dynamical processes of carotenoid excited states. We also discuss the effect of the symmetry-breaking term, , on the internal conversion process, and show that its effect on the extent of internal conversion can be described by a Landau-Zener-type transition. This methodological paper is a companion to our more explanatory discussion of carotenoid excited state dynamics in Manawadu, D.; Georges, T. N.; Barford, W. Photoexcited State Dynamics and Singlet Fission in Carotenoids. J. Phys. Chem. A 2023, 127, 1342.

Target State Optimized Density Functional Theory for Electronic Excited and Diabatic States.

A flexible self-consistent field method, called target state optimization (TSO), is presented for exploring electronic excited configurations and localized diabatic states. The key idea is to partition molecular orbitals into different subspaces according to the excitation or localization pattern for a target state. Because of the orbital-subspace constraint, orbitals belonging to different subspaces do not mix. Furthermore, the determinant wave function for such excited or diabatic configurations can be variationally optimized as a ground state procedure, unlike conventional ΔSCF methods, without the possibility of collapsing back to the ground state or other lower-energy configurations. The TSO method can be applied both in Hartree-Fock theory and in Kohn-Sham density functional theory (DFT). The density projection procedure and the working equations for implementing the TSO method are described along with several illustrative applications. For valence excited states of organic compounds, it was found that the computed excitation energies from TSO-DFT and time-dependent density functional theory (TD-DFT) are of similar quality with average errors of 0.5 and 0.4 eV, respectively. For core excitation, doubly excited states and charge-transfer states, the performance of TSO-DFT is clearly superior to that from conventional TD-DFT calculations. It is shown that variationally optimized charge-localized diabatic states can be defined using TSO-DFT in energy decomposition analysis to gain both qualitative and quantitative insights on intermolecular interactions. Alternatively, the variational diabatic states may be used in molecular dynamics simulation of charge transfer processes. The TSO method can also be used to define basis states in multistate density functional theory for excited states through nonorthogonal state interaction calculations. The software implementing TSO-DFT can be accessed from the authors.

Vibrational response functions for multidimensional electronic spectroscopy in nonadiabatic models.

The interplay of nuclear and electronic dynamics characterizes the multidimensional electronic spectra of various molecular and solid-state systems. Theoretically, the observable effect of such interplay can be accounted for by response functions. Here, we report analytical expressions for the response functions corresponding to a class of model systems. These are characterized by coupling between the diabatic electronic states and the vibrational degrees of freedom, resulting in linear displacements of the corresponding harmonic oscillators, and by nonadiabatic couplings between pairs of diabatic states. In order to derive the linear response functions, we first perform the Dyson expansion of the relevant propagators with respect to the nonadiabatic component of the Hamiltonian, then derive and expand with respect to the displacements the propagators at given interaction times, and finally provide analytical expressions for the time integrals that lead to the different contributions to the linear response function. The approach is then applied to the derivation of third-order response functions describing different physical processes: ground state bleaching, stimulated emission, excited state absorption, and double quantum coherence. Comparisons between the results obtained up to sixth order in the Dyson expansion and independent numerical calculation of the response functions provide evidence of the series convergence in a few representative cases.

Forward-backward electron–proton asymmetry from a two-photon crossing of diabatic states of H[formula omitted] in linearly polarized intense laser field

Controlling spatial–temporal overlap between nuclear wave packets propagating on the coupled electronic states with opposite parity by intense laser field leads to a π periodic modulation in the symmetry breaking of the coupled forward–backward electron and proton motions. The most probable directionality of electron and proton moving simultaneously in opposite directions with total electron–proton asymmetry parameter Ae−ptot=0.62 occurs at fixed carrier-envelope phases of ϑ=15° and 195°. Analysis of the time evolution of the nuclear and the electronic-nuclear wave packets on the field-dressed potentials gives rise to newly insightful images of the nonlinear nonperturbative processes for the asymmetrical localization.

The Marcus dimension: identifying the nuclear coordinate for electron transfer from ab initio calculations.

The Marcus model forms the foundation for all modern discussion of electron transfer (ET). In this model, ET results in a change in diabatic potential energy surfaces, separated along an ET nuclear coordinate. This coordinate accounts for all nuclear motion that promotes electron transfer. It is usually assumed to be dominated by a collective asymmetric vibrational motion of the redox sites involved in the ET. However, this coordinate is rarely quantitatively specified. Instead, it remains a nebulous concept, rather than a tool for gaining true insight into the ET pathway. Herein, we describe an ab initio approach for quantifying the ET coordinate and demonstrate it for a series of dinitroradical anions. Using sampling methods at finite temperature combined with density functional theory calculations, we find that the electron transfer can be followed using the energy separation between potential energy surfaces and the extent of electron localization. The precise nuclear motion that leads to electron transfer is then obtained as a linear combination of normal modes. Once the coordinate is identified, we find that evolution along it results in a change in diabatic state and optical excitation energy, as predicted by the Marcus model. Thus, we conclude that a single dimension of the electron transfer described in Marcus-Hush theory can be described as a well-defined nuclear motion. Importantly, our approach allows the separation of the intrinsic electron transfer coordinate from other structural relaxations and environmental influences. Furthermore, the barrier separating the adiabatic minima was found to be sufficiently thin to enable heavy-atom tunneling in the ET process.

A Comprehensive Approach to Exciton Delocalization and Energy Transfer.

Electrostatic intermolecular interactions lie at the heart of both the Förster model for resonance energy transfer (RET) and the exciton model for energy delocalization. In the Förster theory of RET, the excitation energy incoherently flows from the energy donor to a weakly coupled energy acceptor. The exciton model describes instead the energy delocalization in aggregates of identical (or nearly so) molecules. Here, we introduce a model that brings together molecular aggregates and RET. We will consider a couple of molecules, each described in terms of two diabatic electronic states, coupled to an effective molecular vibration. Electrostatic intermolecular interactions drive energy fluxes between the molecules, that, depending on model parameters, can be described as RET or energy delocalization. At variance with the standard Förster model for RET and of the exciton model for aggregates, our approach applies both in the weak and in the strong coupling regimes and fully accounts for the quantum nature of molecular vibrations in a nonadiabatic approach. Coupling the system to a thermal bath, we follow RET and energy delocalization in real time and simulate time-resolved emission spectra.