Search

Heavy atom compounds represent a challenge for computational chemistry, due to the need for simultaneous treatment of relativistic and correlation effects. Often such systems exhibit also strong correlation which hampers the application of perturbation theory or single-reference coupled cluster (CC) methods. As a viable alternative, we have proposed to externally correct the CC method using the density matrix renormalization group (DMRG) wave functions, yielding the DMRG-tailored CC method. In a previous paper [J. Chem. Phys. {\bf 152}, 174107 (2020)] we have reported a first implementation of this method in the relativistic context, which was restricted to molecules with real double group symmetry. In this work we present a fully general implementation of the method, covering complex and quaternion double groups as well. The 4c-TCC method thus becomes applicable to polyatomic molecules including heavy atoms. For assessment of the method, we performed calculations of the chiral uranium compound NUHFI, which was previously studied in the context of the enhancement of parity violation effects. In particular, we performed calculations of a cut of the potential energy surface of this molecule along the dissociation of the N-U bond, where the system exhibits a strong multireference character. Since there are no experimental data for NUHFI, we have performed also an analogous study of the (more symmetric) NUF$_3$ molecule, where the vibrational frequency of the N-U bond can be compared with spectroscopic data., Comment: 12 pages, 9 figures

We present the implementation of quadratic response theory based upon the relativistic equation-of-motion coupled cluster method. We showcase our implementation, whose generality allows us to consider both time-dependent and time-independent electric and magnetic perturbations, by considering the static and frequency-dependent hyperpolarizability of hydrogen halides (HX, X = F-At), providing a comprehensive insight into their electronic response characteristics. Additionally, we evaluated the Verdet constant for noble gases Xe and Rn, and discussed the relative importance of relativistic and electron correlation effects for these magneto-optical properties. Finally, we calculate the two-photon absorption cross-sections of transition ($ns^{1}S_{0}\to (n+1)s^{1}S_{0}$) of Ga$^{+}$, and In$^{+}$, which are suggested as candidates for new ion clocks. As our implementation allows for the use of non-relativistic Hamiltonians as well, we have compared our EOM-QRCC results to the QR-CC implementation in the DALTON code, and show that the differences between CC and EOMCC response are in general smaller than 5\% for the properties considered. Collectively, the results underscore the versatility of our implementation and its potential as a benchmark tool for other approximated models such as density functional theory for higher-order properties.

We present the development and implementation of the relativistic coupled cluster linear response theory (CC-LR) which allows the determination of molecular properties arising from time-dependent or time-independent electric, magnetic, or mixed electric-magnetic perturbations (within a common gauge origin), and take into account the finite lifetime of excited states via damped response theory. We showcase our implementation, which is capable to offload intensive tensor contractions onto graphical processing units (GPUs), in the calculation of: \textit{(a)} frequency-(in)dependent dipole-dipole polarizabilities of IIB atoms and selected diatomic molecules, with a emphasis on the calculation of valence absorption cross-sections for the I$_2$ molecule;\textit{(b)} indirect spin-spin coupling constants for benchmark systems such as the hydrogen halides (HX, X = F-I) as well the H$_2$Se-H$_2$O dimer as a prototypical system containing hydrogen bonds; and \textit{(c)} optical rotations at the sodium D line for hydrogen peroxide analogues (H$_{2}$Y$_{2}$, Y=O, S, Se, Te). Thanks to this implementation, we are able show the similarities in performance--but often the significant discrepancies--between CC-LR and approximate methods such as density functional theory (DFT). Comparing standard CC response theory with the equation of motion formalism, we find that, for valence properties such as polarizabilities, the two frameworks yield very similar results across the periodic table as found elsewhere in the literature; for properties that probe the core region such as spin-spin couplings, we show a progressive differentiation between the two as relativistic effects become more important. Our results also suggest that as one goes down the periodic table it may become increasingly difficult to measure pure optical rotation at the sodium D line, due to the appearance of absorbing states.

Conical intersections are topologically protected crossings between the potential energy surfaces of a molecular Hamiltonian, known to play an important role in chemical processes such as photoisomerization and non-radiative relaxation. They are characterized by a non-zero Berry phase, which is a topological invariant defined on a closed path in atomic coordinate space, taking the value $\pi$ when the path encircles the intersection manifold. In this work, we show that for real molecular Hamiltonians, the Berry phase can be obtained by tracing a local optimum of a variational ansatz along the chosen path and estimating the overlap between the initial and final state with a control-free Hadamard test. Moreover, by discretizing the path into $N$ points, we can use $N$ single Newton-Raphson steps to update our state non-variationally. Finally, since the Berry phase can only take two discrete values (0 or $\pi$), our procedure succeeds even for a cumulative error bounded by a constant; this allows us to bound the total sampling cost and to readily verify the success of the procedure. We demonstrate numerically the application of our algorithm on small toy models of the formaldimine molecule (\ce{H2C=NH})., Comment: 20 + 7 pages, 4 figures

We report an all-electron, atomic orbital (AO) based, two-component (2C) implementation of the $GW$ approximation (GWA) for closed-shell molecules. Our algorithm is based on the space-time formulation of the GWA and uses analytical continuation of the self-energy, and pair-atomic density fitting (PADF) to switch between AO and auxiliary basis. By calculating the dynamical contribution to the $GW$ self-energy at a quasi-one-component level, our 2C $GW$ algorithm is only about a factor of two to three slower than in the scalar relativistic case. Additionally, we present a 2C implementation of the simplest vertex correction to the self-energy, the statically screened $G3W2$ correction. Comparison of first ionization potentials of a set of 67 molecules with heavy elements (a subset of the SOC81 set) calculated with our implementation against results from the WEST code reveals mean absolute deviations of around 70 meV for $G_0W_0$@PBE and $G_0W_0$@PBE0. These are most likely due to technical differences in both implementations, most notably the use of different basis sets, pseudopotential approximations, different treatment of the frequency dependency of the self-energy and the choice of the 2C-Hamiltonian. Finally, we assess the performance of some (partially self-consistent) variants of the GWA for the calculation of first IPs by comparison to vertical experimental reference values. $G_0W_0$PBE0 (25 \% exact exchange) and $G_0W_0$BHLYP (50 \% exact exchange) perform best with mean absolute deviations (MAD) of about 200 meV. Eigenvalue-only self-consistent $GW$ (ev$GW$) and quasi-particle self-consistent $GW$ (qs$GW$) significantly overestimate the IPs. Perturbative $G3W2$ corrections improve the agreement with experiment in cases where $G_0W_0$ alone underestimates the IPs. With a MAD of only 140 meV, 2C-$G_0W_0$PBE0 + $G3W2$ is in best agreement with the experimental reference values., Comment: Version with recalculated results due to a bug in the code with which the original results where produced

Localized molecular orbitals are often used for the analysis of chemical bonds, but they can also serve to efficiently and comprehensibly compute linear response properties. While conventional canonical molecular orbitals provide an adequate basis for the treatment of excited states, a chemically meaningful identification of the different excited-state processes is difficult within such a delocalized orbital basis. In this work, starting from an initial set of supermolecular canonical molecular orbitals, we provide a simple one-step top-down embedding procedure for generating a set of orbitals which are localized in terms of the supermolecule, but delocalized over each subsystem composing the supermolecule. Using an orbital partitioning scheme based on such sets of localized orbitals, we further present a procedure for the construction of local excitations and charge-transfer states within the linear response framework of time-dependent density functional theory (TDDFT). This procedure provides direct access to approximate diabatic excitation energies and, under the Tamm--Dancoff approximation, also their corresponding electronic couplings -- quantities that are of primary importance in modelling energy transfer processes in complex biological systems. Our approach is compared with a recently developed diabatization procedure based on subsystem TDDFT using projection operators, which leads to a similar set of working equations. Although both of these methods differ in the general localization strategies adopted and the type of basis functions (Slaters vs. Gaussians) employed, an overall decent agreement is obtained.

Pair atomic density fitting (PADF) is a promising strategy to reduce the scaling with system size of quantum chemical methods for the calculation of the correlation energy like the direct random phase approximation (RPA) or second-order M{\o}ller-Plesset perturbation theory (MP2). PADF can however introduce large errors in correlation energies as the two-electron interaction energy is not guaranteed to be bounded from below. This issue can be partially alleviated by using very large fit sets, but this comes at the price of reduced efficiency and having to deal with near-linear dependencies in the fit set. In this work, we introduce an alternative methodology to overcome this problem that preserves the intrinsically favourable scaling of PADF. We first regularize the Fock matrix by projecting out parts of the basis set which gives rise to orbital products that are hard to describe by PADF. We then also apply this projector to the orbital coefficient matrix to improve the precision of PADF-MP2 and PADF-RPA. We systematically assess the accuracy of this new approach in a numerical atomic orbital framework using Slater Type Orbitals (STO) and correlation consistent Gaussian type basis sets up to quintuple-$\zeta$ quality for systems with more than 200 atoms. For the small and medium systems in the S66 database we show the maximum deviation of PADF-MP2 and PADF-RPA relative correlation energies to DF-MP2 and DF-RPA reference results to be 0.07 and 0.14 kcal/mol respectively. When the new projector method is used, the errors only slightly increase for large molecules and also when moderately sized fit sets are used the resulting errors are well under control. Finally, we demonstrate the computational efficiency of our algorithm by calculating the interaction energies of non-covalently bound complexes with more than 1000 atoms and 20000 atomic orbitals at the RPA@PBE/CC-pVTZ level of theory.

The $GW$-Bethe-Salpeter Equation (BSE) method is promising for calculating the low-lying excited states of molecular systems. So far, it has only been applied to rather small molecules, and in the commonly implemented diagonal approximations to the electronic self-energy it depends on a mean-field starting point. We describe here an implementation of the self-consistent and starting-point independent quasiparticle self-consistent (qs$GW$)-BSE approach which is suitable for calculations on large molecules. We herein show that eigenvalue-only self-consistency leads to an unfaithful description of certain excitonic states for Chlorophyll dimers while the qs$GW$-BSE vertical excitation energies (VEE) are in excellent agreement with spectroscopic experiments for Chlorophyll monomers and dimers measured in the gas phase. On the other hand, VEEs from time-dependent density functional theory calculations tend to disagree with experimental values and using different range-separated hybrid (RSH) kernels changes the VEEs by up to 0.5 eV. We use the new qs$GW$-BSE implementation to calculate the lowest excitation energies of the six chromophores of the photosystem II (PSII) reaction center (RC) with nearly 2000 correlated electrons. Using more than 11000 (6000) basis functions, the calculation could be completed in less than 5 (2) days one a single modern compute node. In agreement with previous TD-DFT calculations using RSH kernels on models that do also not include environment effects, our qs$GW$-BSE calculations only yield states with local character in the low-energy spectrum of the hexameric complex. Earlier work with RSH kernels has demonstrated that the protein environment facilitates the experimentally observed interchromophoric charge transfer. Therefore, future research will need to combine correlation effects beyond TD-DFT with an explicit treatment of environment electrostatics.

The high computational scaling with the number of correlated electrons and the size of the basis set is a bottleneck which limits applications of coupled cluster (CC) algorithms. This is particularly so for calculations based on 2- or 4-component relativistic Hamiltonians, which often employ uncontracted basis sets and lead to large virtual molecular orbital (VMO) spaces. This problem may be alleviated by employing a more compact set of virtual spinors than those provided by the canonical Hartree-Fock (HF) set, such as those based on natural orbitals (NOs). In this paper we describe the implementation of a module for generating NOs for correlated wavefunctions, and in particular MP2 frozen natural orbitals (MP2FNOs), as a component of our novel implementation of relativistic coupled cluster theory for massively parallel architectures [J. Pototschnig et. al., J. Chem. Theory Comput. 17, 5509, 2021]. Our implementation is capable of manipulating both complex and quaternion density matrices, thus allowing for the generation of both Kramers-restricted and Kramers-unrestricted MP2FNOs. Furthermore, NOs are re-expressed in the parent atomic orbital (AO) basis, so that the code also makes it possible to generate CCSD natural orbitals in AO basis for further analysis. By investigating the truncation errors of MP2FNOs for both the correlation energy and molecular properties at CCSD level such as the electric field gradients at the nuclei (EFGs), electric dipole and quadrupole moments for hydrogen halides HX (X=F-Ts), and parity-violating energy differences (PV) for H$_2$Y$_2$ (Y=O-Se), we find that MP2FNOs accelerate the convergence of the correlation energy in a roughly uniform manner across the periodic table and that, with VMO spaces truncated to around half the size of the full spaces ones, it is possible to obtain reliable estimates for both energies and all molecular properties considered., Comment: 16 pages, 9 figures

Electron correlation in finite and extended systems is often described in an effective single-particle framework within the $GW$ approximation. Here, we use the statically screened second-order exchange contribution to the self-energy ($G3W2$) to calculate a perturbative correction to the $GW$ self-energy. We use this correction to calculate total correlation energies of atoms, relative energies, as well as charged excitations of a wide range of molecular systems. We show that the second-order correction improves correlation energies with respect to the RPA and also improves relative energies for many, but not all considered systems. While the full $G3W2$ contribution does not give consistent improvements over $GW$, taking the average of $GW$ and $GW + G3W2$ generally gives excellent results. Improvements over quasiparticle self-consistent $GW$, which we show to give very accurate charged excitations in small and medium molecules by itself, are only minor. $G_0W_0$ quasiparticle energies evaluated with eigenvalue and orbitals from range-separated hybrids, however, are tremendously improved upon: The second-order corrected $G_0W_0$ outperforms all existing $GW$ methods for the systems considered herein and also does not come with substantially increased computational cost compared to $G_0W_0$ for systems with up to 100 atoms., Comment: Revised version as accepted by Physical review B (Phys. Rev. B 2022, 105, 125121, 10.1103/PhysRevB.105.125121) Compared to our first submission, a programming mistake in our first implementation has been corrected leading to different (better) results

In this work, we introduce several technical and analytical extensions to our recent state-averaged orbital-optimized variational quantum eigensolver (SA-OO-VQE) algorithm (see Ref. [S. Yalouz et al. ,Quantum Sci. Technol. 6, 024004 (2021).]). Motivated by the limitations of current quantum computers, the first extension consists in an efficient state-resolution procedure to find the SA-OO-VQE eigenstates, and not just the subspace spanned by them, while remaining in the equi-ensemble framework. This approach avoids expensive intermediate resolutions of the eigenstates by postponing this problem to the very end of the full algorithm. The second extension allows for the estimation of analytical gradients and non-adiabatic couplings, which are crucial in many practical situations ranging from the search of conical intersections to the simulation of quantum dynamics, in, for example, photoisomerization reactions. The accuracy of our new implementations is demonstrated on the formaldimine molecule CH$_2$NH (a minimal Schiff base model relevant for the study of photoisomerization in larger bio-molecules), for which we also perform a geometry optimization to locate a conical intersection between the ground and first-excited electronic states of the molecule., Comment: 22 pages, 7 figures

We report an investigation of the low-lying excited states of the YbF molecule--a candidate molecule for experimental measurements of the electron electric dipole moment--with 2-component based multi-reference configuration interaction (MRCI), equation of motion coupled cluster (EOM-CCSD) and the extrapolated intermediate Hamiltonian Fock-space coupled cluster (XIHFS-CCSD). Specifically, we address the question of the nature of these low-lying states in terms of configurations containing filled or partially-filled Yb $4f$ shells. We show that while it does not appear possible to carry out calculations with both kinds of configurations contained in the same active space, reliable information can be extracted from different sectors of Fock space--that is, by performing electron attachment and detachment IHFS-CCSD and EOM-CCSD calculation on the closed-shell YbF$^+$ and YbF$^-$ species, respectively. From these we observe $\Omega = 1/2, 3/2$ states that arise from the $4f^{13}\sigma_{6s}^2$, $4f^{14}5d$/$6p$, and $4f^{13}5d\sigma_{6s}$ configurations appear in the same energy range around the ground-state equilibrium geometry and they are therefore able to interact. As these states are generated from different sectors of Fock space, they are almost orthogonal and provide complementary descriptions of parts of the excited state manifold. To obtain a comprehensive picture, we introduce a simple adiabatization model to extract energies of interacting $\Omega = 1/2, 3/2$ states that can be compared to experimental observations., Comment: 28+57 pages, 8+18 tables, 5+34 figures

We calculate complete basis set (CBS) limit extrapolated ionization potentials (IP) and electron affinities (EA) with Slater Type Basis sets for the molecules in the GW100 database. To this end, we present two new Slater Type orbital (STO) basis sets of triple- (TZ) and quadruple-$\zeta$ (QZ) quality whose polarization is adequate for correlated-electron methods and which contain extra diffuse functions to be able to correctly calculate electron affinities of molecules with a positive Lowest Unoccupied Molecular Orbital (LUMO). We demonstrate, that going from TZ to QZ quality consistently reduces the basis set error of our computed IPs and EAs and we conclude that a good estimate of these quantities at the CBS limit can be obtained by extrapolation. With MADs from 70 to 85 meV, our CBS limit extrapolated ionization potentials are in good agreement with results from FHI-AIMS, TURBOMOLE, VASP and WEST while they differ by more than 130 meV on average from nanoGW. With a MAD of 160 meV, our electron affinities are also in good agreement with the WEST code. Especially for systems with positive LUMOs, the agreement is excellent. With respect to other codes, the STO type basis sets generally underestimate EAs of small molecules with strongly bound LUMOs. With 62 meV for IPs and 93 meV for EAs, we find much better agreement to CBS limit extrapolated results from FHI-AIMS for a set of 250 medium to large organic molecules., Comment: Published open access by Journal of chemical theory and computation

Reducing the complexity of quantum algorithms to treat quantum chemistry problems is essential to demonstrate an eventual quantum advantage of Noisy-Intermediate Scale Quantum (NISQ) devices over their classical counterpart. Significant improvements have been made recently to simulate the time-evolution operator $U(t) = e^{i\mathcal{\hat{H}}t}$ where $\mathcal{\hat{H}}$ is the electronic structure Hamiltonian, or to simulate $\mathcal{\hat{H}}$ directly (when written as a linear combination of unitaries) by using block encoding or "qubitization" techniques. A fundamental measure quantifying the practical implementation complexity of these quantum algorithms is the so-called "1-norm" of the qubit-representation of the Hamiltonian, which can be reduced by writing the Hamiltonian in factorized or tensor-hypercontracted forms for instance. In this work, we investigate the effect of classical pre-optimization of the electronic structure Hamiltonian representation, via single-particle basis transformation, on the 1-norm. Specifically, we employ several localization schemes and benchmark the 1-norm of several systems of different sizes (number of atoms and active space sizes). We also derive a new formula for the 1-norm as a function of the electronic integrals, and use this quantity as a cost function for an orbital-optimization scheme that improves over localization schemes. This paper gives more insights about the importance of the 1-norm in quantum computing for quantum chemistry, and provides simple ways of decreasing its value to reduce the complexity of quantum algorithms.

In this paper, we report a reimplementation of the core algorithms of relativistic coupled cluster theory aimed at modern heterogeneous high-performance computational infrastructures. The code is designed for efficient parallel execution on many compute nodes with optional GPU coprocessing, accomplished via the new ExaTENSOR back end. The resulting ExaCorr module is primarily intended for calculations of molecules with one or more heavy elements, as relativistic effects on electronic structure are included from the outset. In the current work, we thereby focus on exact 2-component methods and demonstrate the accuracy and performance of the software. The module can be used as a stand-alone program requiring a set of molecular orbital coefficients as starting point, but is also interfaced to the DIRAC program that can be used to generate these. We therefore also briefly discuss an improvement of the parallel computing aspects of the relativistic self-consistent field algorithm of the DIRAC program.

In the Noisy Intermediate-Scale Quantum (NISQ) era, solving the electronic structure problem from chemistry is considered as the "killer application" for near-term quantum devices. In spite of the success of variational hybrid quantum/classical algorithms in providing accurate energy profiles for small molecules, careful considerations are still required for the description of complicated features of potential energy surfaces. Because the current quantum resources are very limited, it is common to focus on a restricted part of the Hilbert space (determined by the set of active orbitals). While physically motivated, this approximation can severely impact the description of these complicated features. A perfect example is that of conical intersections (i.e. a singular point of degeneracy between electronic states), which are of primary importance to understand many prominent reactions. Designing active spaces so that the improved accuracy from a quantum computer is not rendered useless is key to finding useful applications of these promising devices within the field of chemistry. To answer this issue, we introduce a NISQ-friendly method called "State-Averaged Orbital-Optimized Variational Quantum Eigensolver" (SA-OO-VQE) which combines two algorithms: (1) a state-averaged orbital-optimizer, and (2) a state-averaged VQE. To demonstrate the success of the method, we classically simulate it on a minimal Schiff base model (namely the formaldimine molecule CH2NH) relevant also for the photoisomerization in rhodopsin -- a crucial step in the process of vision mediated by the presence of a conical intersection. We show that merging both algorithms fulfil the necessary condition to describe the molecule's conical intersection, i.e. the ability to treat degenerate (or quasi-degenerate) states on the same footing., Comment: 18 pages, 7 figures

Localization of molecular orbitals finds its importance in the representation of chemical bonding (and anti-bonding) and in the local correlation treatments beyond mean-field approximation. In this paper, we generalize the intrinsic atomic and bonding orbitals [G. Knizia, J. Chem. Theory Comput. 2013, 9, 11, 4834-4843] to relativistic applications using complex and quaternion spinors, as well as to molecular fragments instead of atomic fragments only. By performing a singular value decomposition, we show how localized valence virtual orbitals can be expressed in this intrinsic minimal basis. We demonstrate our method on systems of increasing complexity, starting from simple cases such as benzene, acrylic-acid and ferrocene molecules, and then demonstrating the use of molecular fragments and inclusion of relativistic effects for complexes containing heavy elements such as tellurium, iridium and astatine. The aforementioned scheme is implemented into a standalone program interfaced with several different quantum chemistry packages.

We derive a low-scaling $G_0W_0$ algorithm for molecules, using pair atomic density fitting (PADF) and an imaginary time representation of the Green's function and describe its implementation in the Slater type orbital (STO) based Amsterdam density functional (ADF) electronic structure code. We demonstrate the scalability of our algorithm on a series of water clusters with up to 432 atoms and 7776 basis functions and observe asymptotic quadratic scaling with realistic threshold qualities controlling distance effects and basis sets of triple-$\zeta$ (TZ) plus double polarization quality. Also owing to a very small prefactor, with these settings a $G_0W_0$ calculation for the largest of these clusters takes only 240 CPU hours. With errors of 0.24 eV for HOMO energies in the GW100 database on the quadruple-$\zeta$ level, our implementation is less accurate than canonical all-electron implementations using the larger def2-QZVP GTO-tpye basis set. Apart from basis set errors, this is related to the well-known shortcomings of the GW space-time method using analytical continuation techniques as well as to numerical issues of the PADF-approach of accurately representing diffuse AO-products. We speculate, that these difficulties might be overcome by using optimized auxiliary fit sets with more diffuse functions of higher angular momenta. Despite these shortcomings, for subsets of medium and large molecules from the GW5000 database, the error of our approach using basis sets of TZ and augmented DZ quality is decreasing with system size. On the augmented DZ level we reproduce canonical, complete basis set limit extrapolated reference values with an accuracy of 80 meV on average for a set of 20 large organic molecules. We anticipate our algorithm, in its current form, to be very useful in the study of single-particle properties of large organic systems such as chromophores and acceptor molecules., Comment: final version as accepted by JCTC https://pubs.acs.org/doi/10.1021/acs.jctc.0c00693

Frozen Density Embedding (FDE) represents a versatile embedding scheme to describe the environmental effect on the electron dynamics in molecular systems. The extension of the general theory of FDE to the real-time time-dependent Kohn-Sham method has previously been presented and implemented in plane-waves and periodic boundary conditions (Pavanello et al. J. Chem. Phys. 142, 154116, 2015). In the current paper, we extend our recent formulation of real-time time-dependent Kohn-Sham method based on localized basis set functions and developed within the Psi4NumPy framework (De Santis et al. J. Chem. Theory Comput. 2020, 16, 2410) to the FDE scheme. The latter has been implemented in its "uncoupled" flavor (in which the time evolution is only carried out for the active subsystem, while the environment subsystems remain at their ground state), using and adapting the FDE implementation already available in the PyEmbed module of the scripting framework PyADF. The implementation was facilitated by the fact that both Psi4NumPy and PyADF, being native Python API, provided an ideal framework of development using the Python advantages in terms of code readability and reusability. We demonstrate that the inclusion of the FDE potential does not introduce any numerical instability in time propagation of the density matrix of the active subsystem and in the limit of weak external field, the numerical results for low-lying transition energies are consistent with those obtained using the reference FDE calculations based on the linear response TDDFT. The method is found to give stable numerical results also in the presence of strong external field inducing non-linear effects.

DIRAC is a freely distributed general-purpose program system for 1-, 2- and 4-component relativistic molecular calculations at the level of Hartree--Fock, Kohn--Sham (including range-separated theory), multiconfigurational self-consistent-field, multireference configuration interaction, coupled cluster and electron propagator theory. At the self-consistent-field level a highly original scheme, based on quaternion algebra, is implemented for the treatment of both spatial and time reversal symmetry. DIRAC features a very general module for the calculation of molecular properties that to a large extent may be defined by the user and further analyzed through a powerful visualization module. It allows the inclusion of environmental effects through three different classes of increasingly sophisticated embedding approaches: the implicit solvation polarizable continuum model, the explicit polarizable embedding, and frozen density embedding models. DIRAC was one of the earliest codes for relativistic molecular calculations and remains a reference in its field., Comment: The following article has been submitted to The Journal of Chemical Physics. After it is published, it will be found at https://aip.scitation.org/toc/jcp/current

The superposition of atomic potentials (SAP) approach has recently been shown to be a simple and efficient way to initialize electronic structure calculations [S. Lehtola, J. Chem. Theory Comput. 15, 1593 (2019)]. Here, we study the differences between effective potentials from fully numerical density functional and optimized effective potential calculations for fixed configurations. We find that the differences are small, overall, and choose exchange-only potentials at the local density approximation level of theory computed on top of Hartree-Fock densities as a good compromise. The differences between potentials arising from different atomic configurations are also found to be small at this level of theory. Furthermore, we discuss the efficient Gaussian-basis implementation of SAP via error function fits to fully numerical atomic radial potentials. The guess obtained from the fitted potentials can be easily implemented in any Gaussian-basis quantum chemistry code in terms of two-electron integrals. Fits covering the whole periodic table from H to Og are reported for non-relativistic as well as fully relativistic four-component calculations that have been carried out with fully numerical approaches., Comment: 12 pages, 8 figures

The NL-eEDM collaboration is building an experimental setup to search for the permanent electric dipole moment of the electron in a slow beam of cold barium fluoride molecules [Eur. Phys. J. D, 72, 197 (2018)]. Knowledge of molecular properties of BaF is thus needed to plan the measurements and in particular to determine an optimal laser-cooling scheme. Accurate and reliable theoretical predictions of these properties require incorporation of both high-order correlation and relativistic effects in the calculations. In this work theoretical investigations of the ground and the lowest excited states of BaF and its lighter homologues, CaF and SrF, are carried out in the framework of the relativistic Fock-space coupled cluster (FSCC) and multireference configuration interaction (MRCI) methods. Using the calculated molecular properties, we determine the Franck-Condon factors (FCFs) for the $A^2\Pi_{1/2} \rightarrow X^2\Sigma^{+}_{1/2}$ transition, which was successfully used for cooling CaF and SrF and is now considered for BaF. For all three species, the FCFs are found to be highly diagonal. Calculations are also performed for the $B^2\Sigma^{+}_{1/2} \rightarrow X^2\Sigma^{+}_{1/2}$ transition recently exploited for laser-cooling of CaF; it is shown that this transition is not suitable for laser-cooling of BaF, due to the non-diagonal nature of the FCFs in this system. Special attention is given to the properties of the $A'^2\Delta$ state, which in the case of BaF causes a leak channel, in contrast to CaF and SrF species where this state is energetically above the excited states used in laser-cooling. We also present the dipole moments of the ground and the excited states of the three molecules and the transition dipole moments (TDMs) between the different states., Comment: Minor changes; The following article has been submitted to the Journal of Chemical Physics. After it is published, it will be found at https://publishing.aip.org/resources/librarians/products/journals/

In the present article, we introduce the relativistic Cholesky-decomposed density (CDD) matrix second-order M{\o}ller-Plesset perturbation theory (MP2) energies. The working equations are formulated in terms of the usual intermediates of MP2 when employing the resolution-of-the-identity approximation (RI) for two-electron integrals. Those intermediates are obtained by substituting the occupied and virtual quaternion pseudo-density matrices of our previously proposed two-component atomic orbital-based MP2 (J. Chem. Phys. 145, 014107 (2016)) by the corresponding pivoted quaternion Cholesky factors. While working within the Kramers-restricted formalism, we obtain a formal spin-orbit overhead of 16 and 28 for the Coulomb and exchange contribution to the 2C MP2 correlation energy, respectively, compared to a non-relativistic (NR) spin-free CDD-MP2 implementation. This compact quaternion formulation could also be easily explored in any other algorithm to compute the 2C MP2 energy. The quaternion Cholesky factors become sparse for large molecules and, with a block-wise screening, block sparse-matrix multiplication algorithm, we observed an effective quadratic scaling of the total wall time for heavy-element containing linear molecules with increasing system size. The total run time for both 1C and 2C calculations was dominated by the contraction to the exchange energy. We have also investigated a bulky Te-containing supramolecular complex. For such bulky, three-dimensionally extended molecules the present screening scheme has a much larger prefactor and is less effective.

We report in this paper an implementation of 4-component relativistic Hamiltonian based Equation-of-Motion Coupled-Cluster with singles and doubles (EOM-CCSD) theory for the calculation of ionization potential (IP), electron affinity (EA) and excitation energy (EE). In this work we utilize previously developed double group symmetry-based generalized tensor contraction scheme, and also extend it in order to carry out tensor contractions involving non-totally symmetric and odd-ranked tensors. Several approximated spin-free and two-component Hamiltonians can also be accessed in this implementation. We have applied this method to the halogen monoxide (XO, X= Cl, Br, I, At, Ts) species, in order to assess the quality of a few other recent EOMCC implementations, where spin-orbit coupling contribution has been approximated in different degree. Besides, we also have studied various excited states of CH$_2$IBr, CH$_2$I$_2$ and I$_2^-$(as well as single electron attachment and detachment electronic states of the same species) where comparison has been made with a closely related multi-reference coupled-cluster method, namely Intermediate Hamiltonian Fock Space Coupled-Cluster singles and doubles (IHFS-CCSD) theory., Comment: improved formatting, added standard deviation for comparisons between eom-ee and fscc(1h1p)

We present a formulation of Laplace-transformed atomic orbital-based second-order M{\o}ller-Plesset perturbation theory (MP2) energies for two-component Hamiltonians in the Kramers-restricted formalism. This low-order scaling technique can be used to enable correlated relativistic calculations for large molecular systems. We show that the working equations to compute the relativistic MP2 energy differ by merely a change of algebra (quaternion instead of real) from their non-relativistic counterparts. With a proof-of-principle implementation we study the effect of the nuclear charge on the magnitude of half-transformed integrals and show that for light elements spin-free and spin-orbit MP2 energies are almost identical. Furthermore, we investigate the effect of separation of charge distributions on the Coulomb and exchange energy con- tributions, which show the same long-range decay with the inter-electronic / atomic distance as for non-relativistic MP2. A linearly scaling implementation is possible if the proper distance behavior is introduced to the quaternion Schwarz-type estimates as for non-relativistic MP2., Comment: accepted for publication in The Journal of Chemical Physics

We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon (AH|FC) method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner's group, very good agreement with TD-DFT calculations using local functionals was achieved., Comment: 14 pages, 19 figures

We propose a new method of calculating electronically excited states that combines a density functional theory (DFT) based ground state calculation with a linear response treatment that employs approximations used in the time-dependent density functional based tight binding (TD-DFTB) approach. The new method termed TD-DFT+TB does not rely on the DFTB parametrization and is therefore applicable to systems involving all combinations of elements. We show that the new method yields UV/Vis absorption spectra that are in excellent agreement with computationally much more expensive time-dependent density functional theory (TD-DFT) calculations. Errors in vertical excitation energies are reduced by a factor of two compared to TD-DFTB., Comment: 14 pages, 6 figures