Spin-restricted Ensemble-referenced Kohn-Sham Research Articles

Formulation of transition dipole gradients for non-adiabatic dynamics with polaritonic states.

A general formulation of the strong coupling between photons confined in a cavity and molecular electronic states is developed for the state-interaction state-average spin-restricted ensemble-referenced Kohn-Sham method. The light-matter interaction is included in the Jaynes-Cummings model, which requires the derivation and implementation of the analytical derivatives of the transition dipole moments between the molecular electronic states. The developed formalism is tested in the simulations of the nonadiabatic dynamics in the polaritonic states resulting from the strong coupling between the cavity photon mode and the ground and excited states of the penta-2,4-dieniminium cation, also known as PSB3. Comparison with the field-free simulations of the excited-state decay dynamics in PSB3 reveals that the light-matter coupling can considerably alter the decay dynamics by increasing the excited state lifetime and hindering photochemically induced torsion about the C=C double bonds of PSB3. The necessity of obtaining analytical transition dipole gradients for the accurate propagation of the dynamics is underlined.

Assessment of the Electron Correlation Treatment on the Quantum-Classical Dynamics of Retinal Protonated Schiff Base Models: XMS-CASPT2, RMS-CASPT2, and REKS Methods.

We compare the performance of three different multiconfigurational wave function-based electronic structure methods and two implementations of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method. The study is characterized by three features: (i) it uses a small set of quantum-classical trajectories rather than potential energy surface mapping, (ii) it focuses, exclusively, on the photoisomerization of retinal protonated Schiff base models, and (iii) it probes the effect of both methyl substitution and the increase in length of the conjugate π-system. For each tested method, the corresponding analytical gradients are used to drive the quantum-classical (Tully's FSSH method) trajectory propagation, including the recent multistate XMS-CASPT2 and RMS-CASPT2 gradients. It is shown that while CASSCF, XMS-CASPT2, and RMS-CASPT2 yield consistent photoisomerization dynamics descriptions, REKS produces, in some of these systems, qualitatively different behavior that is attributed to a flatter and topographically different excited state potential energy surface. The origin of this behavior can be traced back to the effect of the employed density functional approximation. The above studies are further expanded by benchmarking, at the CASSCF and REKS levels, the electronic structure methods using a QM/MM model of the visual pigment rhodopsin.

Calculation of exciton couplings based on density functional tight-binding coupled to state-interaction state-averaged ensemble-referenced Kohn-Sham approach.

We introduce the combination of the density functional tight binding (DFTB) approach, including onsite correction (OC) and long-range corrected (LC) functional and the state-interaction state-averaged spin-restricted ensemble-referenced Kohn-Sham (SI-SA-REKS or SSR) method with extended active space involving four electrons and four orbitals [LC-OC-DFTB/SSR(4,4)], to investigate exciton couplings in multichromophoric systems, such as organic crystals and molecular aggregates. We employ the LC-OC-DFTB/SSR(4,4) method to calculate the excitonic coupling in anthracene and tetracene. As a result, the LC-OC-DFTB/SSR(4,4) method provides a reliable description of the locally excited (LE) state in a single chromophore and the excitonic couplings between chromophores with reasonable accuracy compared to the experiment and the conventional SSR(4,4) method. In addition, the thermal fluctuation of excitonic couplings from dynamic nuclear motion in an anthracene crystal with LC-OC-DFTB/SSR(4,4) shows a similar fluctuation of excitonic coupling and spectral density with those of first-principle calculations. We conclude that LC-OC-DFTB/SSR(4,4) is capable of providing reasonable features related to LE states, such as Frenkel exciton with efficient computational cost.

Generalized Formulation of the Density Functional Tight Binding-Based Restricted Ensemble Kohn-Sham Method with Onsite Correction to Long-Range Correction.

We present a generalized formulation for the combination of the density functional tight binding (DFTB) approach and the state-interaction state-average spin-restricted ensemble-referenced Kohn-Sham (SI-SA-REKS or SSR) method by considering onsite correction (OC) as well as the long-range corrected (LC) functional. The OC contribution provides more accurate energies and analytic gradients for individual microstates, while the multireference character of the SSR provides the correct description for conical intersections. We benchmark the LC-OC-DFTB/SSR method against various DFTB calculation methods for excitation energies and conical intersection structures with π/π* or n/π* characters. Furthermore, we perform excited-state molecular dynamics simulations with a molecular rotary motor with variations of LC-OC-DFTB/SSR approaches. We show that the OC contribution to the LC functional is crucial to obtain the correct geometry of conical intersections.

Machine Learning-Assisted Excited State Molecular Dynamics with the State-Interaction State-Averaged Spin-Restricted Ensemble-Referenced Kohn-Sham Approach.

We present a machine learning-assisted excited state molecular dynamics (ML-ESMD) based on the ensemble density functional theory framework. Since we represent a diabatic Hamiltonian in terms of generalized valence bond ansatz within the state-interaction state-averaged spin-restricted ensemble-referenced Kohn-Sham (SI-SA-REKS) method, we can avoid singularities near conical intersections, which are crucial in excited state molecular dynamics simulations. We train the diabatic Hamiltonian elements and their analytical gradients with the SchNet architecture to construct machine learning models, while the phase freedom of off-diagonal elements of the Hamiltonian is cured by introducing the phase-less loss function. Our machine learning models show reasonable accuracy with mean absolute errors of ∼0.1 kcal/mol and ∼0.5 kcal/mol/Å for the diabatic Hamiltonian elements and their gradients, respectively, for penta-2,4-dieniminium cation. Moreover, by exploiting the diabatic representation, our models can predict correct conical intersection structures and their topologies. In addition, our ML-ESMD simulations give almost identical result with a direct dynamics at the same level of theory.

Computation of Molecular Ionization Energies Using an Ensemble Density Functional Theory Method.

Computation of the ionization energies and of the respective Dyson orbitals based on the use of the extended Koopmans theorem (EKT) is implemented in connection with an ensemble density functional theory (eDFT) method, the state-interaction state-averaged spin-restricted ensemble-referenced Kohn-Sham (SI-SA-REKS or SSR) method. The new methodology enables fast computation of the ionization energies and evaluation of the respective Dyson orbitals, the square norms of which are related with the ionization probabilities, in the ground and excited electronic states of molecules. As the application of EKT recycles the intermediate quantities from the SSR analytical energy gradient, evaluation of the ionization energies and probabilities can be carried out on-the-fly during the nonadiabatic molecular dynamics simulations. This opens up a perspective for fast theoretical simulation of the time-resolved photoelectron spectroscopy observations. In the present work, the new methodology is tested in the computation of the ionization energies and Dyson orbitals of several molecules in the ground and excited electronic states, including strongly correlated species, such as the ozone molecule, dissociating chemical bonds, and conical intersections.

Formulation and Implementation of the Spin-Restricted Ensemble-Referenced Kohn-Sham Method in the Context of the Density Functional Tight Binding Approach.

The spin-restricted ensemble-referenced Kohn-Sham (REKS) method and its state-interaction state-averaged variant (SI-SA-REKS, or SSR) provide computational platform for seamless inclusion of multireference effects into the density functional calculations. The SSR method enables an accurate calculation of the vertical excitation energies for the molecules with multireference ground states and describes conical intersections between the ground and excited states with the accuracy matching the most sophisticated ab initio multireference wave function methods. In this work, the SSR method is formulated and implemented in the context of the long-range corrected density functional tight binding (LC-DFTB) approach. The new LC-DFTB/SSR method enables calculation of the excited electronic states and the S1/S0 conical intersections of very large molecules. The LC-DFTB/SSR method is benchmarked against vertical excitation energies and conical intersection energies and geometries of several organic molecules with π/π* and n/π* transitions. It is demonstrated that the LC-DFTB/SSR method describes these molecules with reasonable accuracy, which can be considerably improved by a slight modification of the LC-DFTB spin polarization parameters.

Direct Nonadiabatic Dynamics by Mixed Quantum-Classical Formalism Connected with Ensemble Density Functional Theory Method: Application to trans-Penta-2,4-dieniminium Cation.

In this work, a direct mixed quantum-classical dynamics approach is presented, which combines two new computational methodologies. The nuclear dynamics is solved by the decoherence-induced surface hopping based on the exact factorization (DISH-XF) method, which is derived from the exact factorization of the electronic-nuclear wave function and correctly describes quantum decoherence phenomena. The state-interaction state-averaged spin-restricted ensemble-referenced Kohn-Sham (SI-SA-REKS, or SSR, for brevity) electronic structure method is based on ensemble density functional theory (eDFT) and provides correct description of real crossings between the ground and excited Born-Oppenheimer electronic states. The new combined approach has been applied to the excited-state nonadiabatic dynamics of the trans-penta-2,4-dieniminium cation (PSB3). The predicted S1 lifetime of trans-PSB3, τ = 99 ± 51 fs, and the quantum yield of the cis conformation, ϕ = 0.63, agree with the results obtained previously in nonadiabatic molecular dynamics simulations performed with a variety of electronic structure methods and dynamics formalisms. Normal-mode analysis of the obtained classical nuclear trajectories suggests that only a few vibrational normal modes contribute to the nuclear wavepacket; where synchronization between several modes plays a dominant role for the outcome of photoisomerization.

Description of ground and excited electronic states by ensemble density functional method with extended active space.

An extended variant of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, the REKS(4,4) method, designed to describe the ground electronic states of strongly multireference systems is modified to enable calculation of excited states within the time-independent variational formalism. The new method, the state-interaction state-averaged REKS(4,4), i.e., SI-SA-REKS(4,4), is capable of describing several excited states of a molecule involving double bond cleavage, polyradical character, or multiple chromophoric units. We demonstrate that the new method correctly describes the ground and the lowest singlet excited states of a molecule (ethylene) undergoing double bond cleavage. The applicability of the new method for excitonic states is illustrated with π stacked ethylene and tetracene dimers. We conclude that the new method can describe a wide range of multireference phenomena.

Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs.

The spin-restricted ensemble-referenced Kohn-Sham (REKS) method is based on an ensemble representation of the density and is capable of correctly describing the non-dynamic electron correlation stemming from (near-)degeneracy of several electronic configurations. The existing REKS methodology describes systems with two electrons in two fractionally occupied orbitals. In this work, the REKS methodology is extended to treat systems with four fractionally occupied orbitals accommodating four electrons and self-consistent implementation of the REKS(4,4) method with simultaneous optimization of the orbitals and their fractional occupation numbers is reported. The new method is applied to a number of molecular systems where simultaneous dissociation of several chemical bonds takes place, as well as to the singlet ground states of organic tetraradicals 2,4-didehydrometaxylylene and 1,4,6,9-spiro[4.4]nonatetrayl.

Ensemble density functional theory method correctly describes bond dissociation, excited state electron transfer, and double excitations.

State-averaged (SA) variants of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, SA-REKS and state-interaction (SI)-SA-REKS, implement ensemble density functional theory for variationally obtaining excitation energies of molecular systems. In this work, the currently existing version of the SA-REKS method, which included only one excited state into the ensemble averaging, is extended by adding more excited states to the averaged energy functional. A general strategy for extension of the REKS-type methods to larger ensembles of ground and excited states is outlined and implemented in extended versions of the SA-REKS and SI-SA-REKS methods. The newly developed methods are tested in the calculation of several excited states of ground-state multi-reference systems, such as dissociating hydrogen molecule, and excited states of donor-acceptor molecular systems. For hydrogen molecule, the new method correctly reproduces the distance dependence of the lowest excited state energies and describes an avoided crossing between the doubly excited and singly excited states. For bithiophene-perylenediimide stacked complex, the SI-SA-REKS method correctly describes crossing between the locally excited state and the charge transfer excited state and yields vertical excitation energies in good agreement with the ab initio wavefunction methods.

Ensemble DFT Approach to Excited States of Strongly Correlated Molecular Systems.

Ensemble density functional theory (DFT) is a novel time-independent formalism for obtaining excitation energies of many-body fermionic systems. A considerable advantage of ensemble DFT over the more common Kohn-Sham (KS) DFT and time-dependent DFT formalisms is that it enables one to account for strong non-dynamic electron correlation in the ground and excited states of molecular systems in a transparent and accurate fashion. Despite its positive aspects, ensemble DFT has not so far found its way into the repertoire of methods of modern computational chemistry, probably because of the perceived lack of practically affordable implementations of the theory. The spin-restricted ensemble-referenced KS (REKS) method is perhaps the first computationally feasible implementation of the ideas behind ensemble DFT which enables one to describe accurately electronic transitions in a wide class of molecular systems, including strongly correlated molecules (biradicals, molecules undergoing bond breaking/formation), extended π-conjugated systems, donor-acceptor charge transfer adducts, etc.

Description of electron transfer in the ground and excited states of organic donor-acceptor systems by single-reference and multi-reference density functional methods.

Electron transfer in the ground and excited states of a model donor-acceptor (D-A) system is investigated using the single-reference and multi-reference density functional theory (DFT) methods. To analyze the results of the calculations, a simple two-site multi-reference model was derived that predicts a stepwise electron transfer in the S0 state and a wave-like dependence of the S1 electron transfer on the external stimulus. The standard single-reference Kohn-Sham (KS) DFT approach and the time-dependent DFT (TDDFT) method failed to describe the correct dependence of the S0 and S1 electron transfer on the external electric field applied along the donor-acceptor system. The multi-reference DFT approach, the spin-restricted ensemble-referenced KS (REKS) method, was able to successfully reproduce the correct behavior of the S0 and S1 electron transfer on the applied field. The REKS method was benchmarked against experimentally measured gas phase charge transfer excitations in a series of organic donor-acceptor complexes and displayed its ability to describe this type of electronic transitions with a very high accuracy, mean absolute error of 0.05 eV with the use of the standard range separated density functionals. On the basis of the calculations undertaken in this work, it is suggested that the non-adiabatic coupling between the S0 and S1 states may interfere with the electron transfer in a weakly coupled donor-acceptor system. It is also suggested that the electronic excitation of a D(+)-A(-) system may play a dual role by assisting the further electron transfer at certain magnitudes of the applied electric field and causing the backward transfer at lower electric field strengths.

Excitation Energies from Spin-Restricted Ensemble-Referenced Kohn−Sham Method: A State-Average Approach

A time-independent density functional approach to the calculation of excitation energies from the ground states of molecules typified by the strong nondynamic electron correlation is suggested. The new method is based on the use of the spin-restricted ensemble-referenced Kohn-Sham formalism [Filatov, M.; Shaik, S. Chem. Phys. Lett. 1999, 304, 429] for the calculation of the ground state. In the new method, the average energy of the ground state and a state created by a single excitation thereof is minimized with respect to the Kohn-Sham orbitals and their fractional occupation numbers. The lowest singlet excitation energies obtained with the help of the new formalism for a number of model systems, such as the hydrogen molecule with stretched bond, twisted ethylene, and twisted hexa-1,3,5-triene, are compared with the results of the time-dependent density functional theory, with the results of ab initio CASSCF/CASPT2 calculations, and with the experimental data. Applicability of the new method to the description of photochemical reactions is discussed.

Restricted Ensemble-Referenced Kohn-Sham versus Broken Symmetry Approaches in Density Functional Theory: Magnetic Coupling in Cu Binuclear Complexes.

The performance of density functional theory in estimating the magnetic coupling constant in a series of Cu(II) binuclear complexes is investigated by making use of two open shell formalisms: the broken symmetry and the spin-restricted ensemble-referenced Kohn-Sham methods. The strong dependence of the calculated magnetic coupling constants with respect to the exchange-correlation functional is confirmed and found to be independent of whether spin symmetry is imposed or not. The use of a method which guarantees the spin state does not improve the correlation with the experiment and indeed shows some worsening due to an overestimation of the ferromagnetic interactions. However, with the present exchange-correlation functionals, a rather systematic deviation is found. Therefore, it would be possible to develop improved density functionals which will allow for a rigorous treatment of open shell systems in density functional theory.