Complete Active Space Configuration Interaction Research Articles

Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory.

Polariton chemistry has attracted great attention as a potential route to modify chemical structure, properties, and reactivity through strong interactions among molecular electronic, vibrational, or rovibrational degrees of freedom. A rigorous theoretical treatment of molecular polaritons requires the treatment of matter and photon degrees of freedom on equal quantum mechanical footing. In the limit of molecular electronic strong or ultrastrong coupling to one or a few molecules, it is desirable to treat the molecular electronic degrees of freedom using the tools of ab initio quantum chemistry, yielding an approach we refer to as ab initio cavity quantum electrodynamics, where the photon degrees of freedom are treated at the level of cavity quantum electrodynamics. Here, we present an approach called Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction theory to provide ground- and excited-state polaritonic surfaces with a balanced description of strong correlation effects among electronic and photonic degrees of freedom. This method provides a platform for ab initio cavity quantum electrodynamics when both strong electron correlation and strong light-matter coupling are important and is an important step toward computational approaches that yield multiple polaritonic potential energy surfaces and couplings that can be leveraged for ab initio molecular dynamics simulations of polariton chemistry.

Simulating the Excited-State Dynamics of Polaritons with Ab Initio Multiple Spawning.

Over the past decade, there has been a growth of interest in polaritonic chemistry, where the formation of hybrid light-matter states (polaritons) can alter the course of photochemical reactions. These hybrid states are created by strong coupling between molecules and photons in resonant optical cavities and can even occur in the absence of light when the molecule is strongly coupled with the electromagnetic fluctuations of the vacuum field. We present a first-principles model to simulate nonadiabatic dynamics of such polaritonic states inside optical cavities by leveraging graphical processing units (GPUs). Our first implementation of this model is specialized for a single molecule coupled to a single-photon mode confined inside the optical cavity but with any number of excited states computed using complete active space configuration interaction (CASCI) and a Jaynes-Cummings-type Hamiltonian. Using this model, we have simulated the excited-state dynamics of a single salicylideneaniline (SA) molecule strongly coupled to a cavity photon with the ab initio multiple spawning (AIMS) method. We demonstrate how the branching ratios of the photodeactivation pathways for this molecule can be manipulated by coupling to the cavity. We also show how one can stop the photoreaction from happening inside of an optical cavity. Finally, we also investigate cavity-based control of the ordering of two excited states (one optically bright and the other optically dark) inside a cavity for a set of molecules, where the dark and bright states are close in energy.

Quantum Information-Assisted Complete Active Space Optimization (QICAS).

We propose an effective quantum information-assisted complete active space optimization scheme (QICAS). What sets QICAS apart from other correlation-based selection schemes is (i) the use of unique measures from quantum information that assess the correlation in electronic structures in an unambiguous and predictive manner and (ii) an orbital optimization step that minimizes the correlation discarded by the active space approximation. Equipped with these features, QICAS yields, for smaller correlated molecule, sets of optimized orbitals with respect to which the complete active space configuration interaction energy reaches the corresponding complete active space self-consistent field (CASSCF) energy within chemical accuracy. For more challenging systems such as the chromium dimer, QICAS offers an excellent starting point for CASSCF by greatly reducing the number of iterations required for numerical convergence. Accordingly, our study validates a profound empirical conjecture: the energetically optimal nonactive spaces are predominantly those that contain the least entanglement.

Ultrafast internal conversion and photochromism in gas-phase salicylideneaniline.

Salicylideneaniline (SA) is an archetypal system for excited-state intramolecular proton transfer (ESIPT) in non-planar systems. Multiple channels for relaxation involving both the keto and enol forms have been proposed after excitation to S1 with near-UV light. Here, we present transient absorption measurements of hot gas-phase SA, jet-cooled SA, and SA in Ar clusters using cavity-enhanced transient absorption spectroscopy (CE-TAS). Assignment of the spectra is aided by simulated TAS spectra, computed by applying time-dependent complete active space configuration interaction (TD-CASCI) to structures drawn from nonadiabatic molecular dynamics simulations. We find prompt ESIPT in all conditions followed by the rapid generation of the trans keto metastable photochrome state and fluorescent keto state in parallel. Increasing the internal energy increases the photochrome yield and decreases the fluorescent yield and fluorescent state lifetime observed in TAS. In Ar clusters, internal conversion of SA is severely hindered, but the photochrome yield is unchanged. Taken together, these results are consistent with the photochrome being produced via the vibrationally excited keto population after ESIPT.

A quantum computing implementation of nuclearelectronic orbital (NEO) theory: Toward an exact pre-Born-Oppenheimer formulation of molecular quantum systems.

Nuclear quantum phenomena beyond the Born-Oppenheimer approximation are known to play an important role in a growing number of chemical and biological processes. While there exists no unique consensus on a rigorous and efficient implementation of coupled electron-nuclear quantum dynamics, it is recognized that these problems scale exponentially with system size on classical processors and, therefore, may benefit from quantum computing implementations. Here, we introduce a methodology for the efficient quantum treatment of the electron-nuclear problem on near-term quantum computers, based upon the Nuclear-Electronic Orbital (NEO) approach. We generalize the electronic two-qubit tapering scheme to include nuclei by exploiting symmetries inherent in the NEO framework, thereby reducing the Hamiltonian dimension, number of qubits, gates, and measurements needed for calculations. We also develop parameter transfer and initialization techniques, which improve convergence behavior relative to conventional initialization. These techniques are applied to H2 and malonaldehyde for which results agree with NEO full configuration interaction and NEO complete active space configuration interaction benchmarks for ground state energy to within 10-6 hartree and entanglement entropy to within 10-4. These implementations therefore significantly reduce resource requirements for full quantum simulations of molecules on near-term quantum devices while maintaining high accuracy.

Beyond energetic and scalar measures: Next generation quantum theory of atoms in molecules

AbstractNext generation quantum theory of atoms in molecules (NG‐QTAIM) is currently the only vector‐based quantum chemical theory as all other quantum chemical theories are scalar‐based. NG‐QTAIM can, for instance, be used to distinguish enantiomers, isotopomers undergoing normal modes of vibration, predict ring‐opening reaction products, ground and excited states at a conical intersection and predict reaction pathways of permutation‐inversion isomers. As a consequence, NG‐QTAIM can uniquely be used to investigate iso‐energetic phenomena where the reliance on differences in geometric measures is removed. NG‐QTAIM has already been used to determine molecular chirality consistent with the Cahn–Ingold–Prelog (CIP) classifications for chiral molecules in addition to the reactant and product of a chiral SN2 reaction. The CIP classifications however, cannot quantify the chirality of intermediate reaction structures due to their formally achiral nature. We identify the presence of chirality by quantifying a helical response of the bond electrons consistent with photoexcitation circular dichroism experiments that utilize the helical motion of the bound electrons for chiral discrimination. NG‐QTAIM can also be used to provide nongeometric based reasoning as to why there are stronger hydrogen‐bonds in cyclic water clusters compared with compact water clusters. Additionally, the effects of electric‐fields and laser irradiation in conditions not amenable to explanation using scalar measures are quantified. The QuantVec software is introduced, which coordinates external programs and efficiently computes the NG‐QTAIM analyses using the wavefunctions from a wide range of ground and excited states computed with DFT, coupled‐cluster, complete active space SCF, configuration interaction, or quantum dynamics methods.This article is categorized under: Structure and Mechanism > Molecular Structures Structure and Mechanism > Reaction Mechanisms and Catalysis Software > Quantum Chemistry

Floquet Time-Dependent Configuration Interaction for Modeling Ultrafast Electron Dynamics

Time-dependent electronic structure methods are a valuable tool for simulating spectroscopic experiments. Recent advances in time-dependent configuration interaction (TDCI) algorithms have made them an attractive means of modeling many-electron dynamics, particularly for cases where multireference effects are essential. Here we present an extension to TDCI, Floquet TDCI, where the electronic wave function is expanded in a basis of light-dressed determinants. Our approach is based on our high-performance graphics processing unit (GPU) accelerated implementation of complete active space configuration interaction (CASCI). Simulations of two-photon absorption demonstrate that Floquet TDCI is well-suited for modeling dynamics in intense, ultrashort laser pulses. Accurate results are obtained for pulse energies up to ∼4 × 10-4 J/cm2 per pulse in the most difficult case explored here. By simulation of a set of molecules under continuous wave coupling, we demonstrate the ability of Floquet to describe the entanglement of light and multiple molecules in a cavity (i.e., a cavity polariton). Excellent computational performance is observed: a 320 fs propagation of a large dye (C30N2H22) with a 2 as timestep and a large active space (10 electrons in 11 orbitals), including a monochromatic pulse with three photon states, was performed in 3 h 6 min on a single Tesla V100 GPU. Our Floquet TDCI algorithm scales linearly with the number of photon states and exponentially with the number of photon colors included in the calculation. We argue that its energy-conserving nature makes Floquet TDCI well-suited to drive nonadiabatic molecular dynamics simulations.

Simulation of adiabatic quantum computing for molecular ground states.

Quantum computation promises to provide substantial speedups in many practical applications with a particularly exciting one being the simulation of quantum many-body systems. Adiabatic state preparation (ASP) is one way that quantum computers could recreate and simulate the ground state of a physical system. In this paper, we explore a novel approach for classically simulating the time dynamics of ASP with high accuracy and with only modest computational resources via an adaptive sampling configuration interaction scheme for truncating the Hilbert space to only the most important determinants. We verify that this truncation introduces negligible error and use this new approach to simulate ASP for sets of small molecular systems and Hubbard models. Furthermore, we examine two approaches to speeding up ASP when performed on quantum hardware: (i) using the complete active space configuration interaction (CASCI) wave function instead of the Hartree-Fock initial state and (ii) a nonlinear interpolation between the initial and target Hamiltonians. We find that starting with a CASCI wave function with a limited active space yields substantial speedups for many of the systems examined, while nonlinear interpolation does not. In additional, we observe interesting trends in the minimum gap location (based on the initial state) as well as how state preparation time can depend on certain molecular properties, such as the number of valence electrons. Importantly, we find that the required state preparation times do not show an immediate exponential wall that would preclude an efficient run of ASP on actual hardware.

An efficient implementation of the NEVPT2 and CASPT2 methods avoiding higher-order density matrices.

A factorization of the matrix elements of the Dyall Hamiltonian in N-electron valence state perturbation theory allowing their evaluation with a computational effort comparable to the one needed for the construction of the third-order reduced density matrix at the most is presented. Thus, the computational bottleneck arising from explicit evaluation of the fourth-order density matrix is avoided. It is also shown that the residual terms arising in the case of an approximate complete active space configuration interaction solution and containing even the fifth-order density matrix for two excitation classes can be evaluated with little additional effort by choosing again a favorable factorization of the corresponding matrix elements. An analogous argument is also provided for avoiding the fourth-order density matrix in complete active space second-order perturbation theory. Practical calculations indicate that such an approach leads to a considerable gain in computational efficiency without any compromise in numerical accuracy or stability.

Extraction of a One-Particle Reduced Density Matrix from a Quantum Monte Carlo Electronic Density: A New Tool for Studying Nondynamic Correlation

In this work, we present a method to build a first order reduced density matrix (1-RDM) of a molecule from variational Quantum Monte Carlo (VMC) computations by means of a given correlated mapping wave function. Such a wave function is modeled on a Generalized Valence Bond plus Complete Active Space Configuration Interaction form and fits at best the density resulting from the Slater-Jastrow wave function of VMC. The accuracy of the method proposed has been proved by comparing the resulting kinetic energy with the corresponding VMC value. This 1-RDM is used to analyze the amount of correlation eventually captured in Kohn-Sham calculations performed in an unrestricted approach (UKS-DFT) and with different energy functionals. We performed test calculations on a selected set of molecules that show a significant multireference character. In this analysis, we compared both local and global indicators of nondynamic and dynamic correlation. Moreover, following the natural orbital decomposition of the 1-RDM, we also compared the effective temperatures of the corresponding Fermi-like distributions. Although there is a general agreement between UKS-DFT and VMC, we found the best match with the functional LC-BLYP.

Active Learning Configuration Interaction for Excited-State Calculations of Polycyclic Aromatic Hydrocarbons.

We present the active learning configuration interaction (ALCI) method for multiconfigurational calculations based on large active spaces. ALCI leverages the use of an active learning procedure to find important electronic configurations among the full configurational space generated within an active space. We tested it for the calculation of singlet–singlet excited states of acenes and pyrene using different machine learning algorithms. The ALCI method yields excitation energies within 0.2–0.3 eV from those obtained by traditional complete active-space configuration interaction (CASCI) calculations (affordable for active spaces up to 16 electrons in 16 orbitals) by including only a small fraction of the CASCI configuration space in the calculations. For larger active spaces (we tested up to 26 electrons in 26 orbitals), not affordable with traditional CI methods, ALCI captures the trends of experimental excitation energies. Overall, ALCI provides satisfactory approximations to large active-space wave functions with up to 10 orders of magnitude fewer determinants for the systems presented here. These ALCI wave functions are promising and affordable starting points for the subsequent second-order perturbation theory or pair-density functional theory calculations.

Complete-active-space extended Koopmans theorem method

The complete-active-space (CAS) extended Koopmans theorem (EKT) method is defined as a special case of the EKT in which the reference state is a CAS configuration interaction (CI) expansion and the electron removal operator acts only on the active orbitals. With these restrictions, the EKT is equivalent to the CI procedure involving all hole-state configurations derived from the active space of the reference wavefunction and has properties analogous to those of the original Koopmans theorem. The equivalence is used to demonstrate in a transparent manner that the first ionization energy predicted by the EKT is in general not exact, i.e., not equal to the difference between the full CI energies of the neutral and the ion, but can approach the full CI result with arbitrary precision even within a finite basis set. The findings also reconcile various statements about the EKT found in the literature.

Calculation of the Zeeman Effect for Transition-Metal Complexes by Multiconfiguration Pair-Density Functional Theory.

Spin-orbit coupling is especially critical for the description of magnetic anisotropy, electron paramagnetic resonance spectroscopy of inorganic radicals and transition-metal complexes, and intersystem crossing. Here, we show how spin-orbit coupling may be included in multiconfiguration pair-density functional theory (MC-PDFT), and we apply the resulting formulation to the calculation of magnetic g tensors (which govern the Zeeman effect) of molecules containing transition metals. MC-PDFT is an efficient method for including static and dynamic electronic correlation in the quantum mechanical treatment of molecules; here, we apply it with spin-orbit coupling by using complete active space self-consistent field (CASSCF) and complete active space configuration interaction (CASCI) wave functions and on-top density functionals. We propose a systematic CASCI scheme for the g tensor calculation of the ground state of the systems under consideration, and we show its superiority over the conventional CASSCF scheme. State interaction, which is important for degenerate and nearly degenerate states, is included by extended multi-state PDFT (XMS-PDFT). Applications are reported for the ground doublet states of 25 transition-metal complexes with d1, d5, d7, and d9 configurations. The MC-PDFT methods are shown to be both efficient and accurate as compared with complete active space second-order perturbation theory.

CAS without SCF-Why to use CASCI and where to get the orbitals.

The complete active space self-consistent field (CASSCF) method has seen broad adoption due to its ability to describe the electronic structure of both the ground and excited states of molecules over a broader swath of the potential energy surface than is possible with the simpler Hartree-Fock approximation. However, it also has a reputation for being unwieldy, computationally costly, and un-black-box. Here, we discuss a class of alternatives, complete active space configuration interaction (CASCI) methods, paying particular attention to their application to electronic excited states. The goal of this Perspective is fourfold. First, we argue that CASCI is not merely an approximation to CASSCF, in that it can be designed to have important qualitative advantages over CASSCF. Second, we present several insights drawn from our experience experimenting with different schemes for computing orbitals to be employed in CASCI. Third, we argue that CASCI is well suited for application to nanomaterials. Finally, we reason that, with the rise in new low-scaling approaches for describing multireference systems, there is a greater need than ever to develop new methods for defining orbitals that provide an efficient and accurate description of both static correlation and electronic excitations in a limited active space.

Electron scattering from HNCO

In this article we report the results of ab-initio R-matrix calculations for low energy e-HNCO scattering processes such as elastic, electronic excitation, and dissociation. The processes are investigated using static exchange with polarisation and complete active space-configuration interaction models. Formation of resonance is observed in elastic and electronic excitation channels. The resonances are studied and characterized for the first time for the present target molecule.

Electron scattering studies of BF and BF2

The present article reports calculated elastic, differential, momentum transfer and excitation cross section for electron scattering from BF and BF2 radicals using the ab initio R-matrix method. The calculations are performed with complete active space—configuration interaction and static exchange models for both targets to yield scattering cross sections and resonance parameters. Elastic and momentum transfer cross sections are also calculated using the spherical complex optical potential method to cover a wide energy range. The total ionization cross section is also reported from ionization threshold to 5 keV. The calculated cross sections for these neutral species are important for BF3 plasma and are reported for the first time to the best of our knowledge except ionization.

Taming the excited states of butadiene, hexatriene, and octatetraene using state specific multireference perturbation theory with density functional theory orbitals.

To compute the electronic excitation energies, a state-specific multireference Møller-Plesset perturbation theory (SSMRPT) with a complete active space configuration interaction reference function constructed using the orbitals obtained by the density functional theory (DFT) is presented as an accurate, as well as computationally affordable, and efficient protocol at the level of second order. The global hybrid B3LYP (Becke, 3-parameter, Lee-Yang-Parr) functional has been used to generate orbitals. The present method, called DFT-SSMRPT, uses perturbers that are individual Slater determinants and accounts for the coupling between the nondynamical and dynamical correlation effects. We have applied the new method to compute excitation energies in conjugated systems of π-electrons such as trans-1,3-butadiene, trans,trans-1,3,5-hexatriene, and all-trans-1,3,5,7-octatetraene. The ordering of the excited states is correctly reproduced by the DFT-SSMRPT calculations. The relative ordering of low-lying excited 1Bu and 1Ag states alters when the length of the polyene changes. The results match reasonably well with the literature including experimental and best theoretical findings. The accuracy of the method is sufficient to discern the energy gap between the close low-lying singlet and triplet states. The DFT-SSMRPT appears as an affordable computational ab initio avenue for a qualitatively correct description of excitation energies.

Molecular Design Principle for Efficient Singlet Fission Based on Diradical Characters and Exchange Integrals: Multiple Heteroatom Substitution Effect on Anthracenes

We theoretically investigate significant impacts of diradical characters and exchange integrals on the first singlet (S1) and triplet (T1) excitation energies related to singlet fission (SF), from which a series of C2h-symmetrically diazadibora-substituted anthracenes [(BN)2-anthracenes] are newly proposed as potential efficient SF chromophores. From the analytical expressions of electronic structures for a model system with two electrons in two orbitals, a tuning of exchange integrals represented by localized natural orbitals is shown to be effective to vary E(S1) and E(T1), in addition to the control of diradical characters, both of which are expected to result in SF isothermal or exothermic [E(S1) – 2E(T1) ≈ 0 or > 0]. The applicability of this strategy to realistic molecules is verified for multiple heteroatom substitution to anthracene, namely, (BN)2-anthracenes, by the complete active space configuration interaction method and the time-dependent density functional theory method. Our calculations show that (BN)2-anthracenes exhibit a wide range of diradical characters and enhanced exchange integrals, enabling flexible tunings of E(S1) and E(T1). Accordingly, several (BN)2-anthracenes are found to be promising candidates for efficient SF. Such a behavior of diradical character can be understood from resonance structures associated with the captodative effect. Moreover, a concrete strategy of tuning exchange integrals is demonstrated in terms of frontier molecular orbital distributions. The present results open up novel molecular design guidelines for efficient SF based on the tuning of exchange integrals in addition to diradical characters.

Artificial Neural Networks Applied as Molecular Wave Function Solvers.

We use artificial neural networks (ANNs) based on the Boltzmann machine (BM) architectures as an encoder of ab initio molecular many-electron wave functions represented with the complete active space configuration interaction (CAS-CI) model. As first introduced by the work of Carleo and Troyer for physical systems, the coefficients of the electronic configurations in the CI expansion are parametrized with the BMs as a function of their occupancies that act as descriptors. This ANN-based wave function ansatz is referred to as the neural-network quantum state (NQS). The machine learning is used for training the BMs in terms of finding a variationally optimal form of the ground-state wave function on the basis of the energy minimization. It is relevant to reinforcement learning and does not use any reference data nor prior knowledge of the wave function, while the Hamiltonian is given based on a user-specified chemical structure in the first-principles manner. Carleo and Troyer used the restricted Boltzmann machine (RBM), which has hidden units, for the neural network architecture of NQS, while, in this study, we further introduce its replacement with the BM that has only visible units but with different orders of connectivity. For this hidden-node free BM, the second- and third-order BMs based on quadratic and cubic energy functions, respectively, were implemented. We denote these second- and third-order BMs as BM2 and BM3, respectively. The pilot implementation of the NQS solver into an exact diagonalization module of the quantum chemistry program was made to assess the capability of variants of the BM-based NQS. The test calculations were performed by determining the CAS-CI wave functions of illustrative molecular systems, indocyanine green, and dinitrogen dissociation. The simulated energies have been shown to converge to CAS-CI energy in most cases by improving RBM with an increasing number of hidden nodes. BM3 systematically yields lower energies than BM2, reproducing the CAS-CI energies of dinitrogen across potential energy curves within an error of 50 μEh.

Mechanism of L2,3-edge x-ray magnetic circular dichroism intensity from quantum chemical calculations and experiment-A case study on V(IV)/V(III) complexes.

In this work, we present a combined experimental and theoretical study on the V L2,3-edge x-ray absorption (XAS) and x-ray magnetic circular dichroism (XMCD) spectra of VIVO(acac)2 and VIII(acac)3 prototype complexes. The recorded V L2,3-edge XAS and XMCD spectra are richly featured in both V L3 and L2 spectral regions. In an effort to predict and interpret the nature of the experimentally observed spectral features, a first-principles approach for the simultaneous prediction of XAS and XMCD spectra in the framework of wavefunction based ab initio methods is presented. The theory used here has previously been formulated for predicting optical absorption and MCD spectra. In the present context, it is applied to the prediction of the V L2,3-edge XAS and XMCD spectra of the VIVO(acac)2 and VIII(acac)3 complexes. In this approach, the spin-free Hamiltonian is computed on the basis of the complete active space configuration interaction (CASCI) in conjunction with second order N-electron valence state perturbation theory (NEVPT2) as well as the density functional theory (DFT)/restricted open configuration interaction with singles configuration state functions based on a ground state Kohn-Sham determinant (ROCIS/DFT). Quasi-degenerate perturbation theory is then used to treat the spin-orbit coupling (SOC) operator variationally at the many particle level. The XAS and XMCD transitions are computed between the relativistic many particle states, considering their respective Boltzmann populations. These states are obtained from the diagonalization of the SOC operator along with the spin and orbital Zeeman operators. Upon averaging over all possible magnetic field orientations, the XAS and XMCD spectra of randomly oriented samples are obtained. This approach does not rely on the validity of low-order perturbation theory and provides simultaneous access to the calculation of XMCD A, B, and C terms. The ability of the method to predict the XMCD C-term signs and provide access to the XMCD intensity mechanism is demonstrated on the basis of a generalized state coupling mechanism based on the type of the excitations dominating the relativistically corrected states. In the second step, the performance of CASCI, CASCI/NEVPT2, and ROCIS/DFT is evaluated. The very good agreement between theory and experiment has allowed us to unravel the complicated XMCD C-term mechanism on the basis of the SOC interaction between the various multiplets with spin S' = S, S ± 1. In the last step, it is shown that the commonly used spin and orbital sum rules are inadequate in interpreting the intensity mechanism of the XAS and XMCD spectra of the VIVO(acac)2 and VIII(acac)3 complexes as they breakdown when they are employed to predict their magneto-optical properties. This conclusion is expected to hold more generally.