1,721,041 research outputs found
A black-box, general purpose quadratic self-consistent field code with and without Cholesky decomposition of the two-electron integrals
Full text linkWe present the implementation of a quadratically convergent self-consistent field (QCSCF) algorithm based on an adaptive trust-radius optimisation scheme for restricted open-shell Hartree–Fock (ROHF), restricted Hartree–Fock (RHF), and unrestricted Hartree–Fock (UHF) references. The algorithm can exploit Cholesky decomposition (CD) of the two-electron integrals to allow calculations on larger systems. The most important feature of the QCSCF code lies in its black-box nature–probably the most important quality desired by a generic user. As shown for pilot applications, it does not require one to tune the self-consistent field (SCF) parameters (damping, Pulay's DIIS, and other similar techniques) in difficult-to-converge molecules. Also, it can be used to obtain a very tight convergence with extended basis sets–a situation often needed when computing high-order molecular properties–where the standard SCF algorithm starts to oscillate. Nevertheless, trouble may appear even with a QCSCF solver. In this respect, we discuss what can go wrong, focusing on the multiple UHF solutions of ortho-benzyne
Excited state Born-Oppenheimer molecular dynamics through coupling between time dependent DFT and AMOEBA
Full text linkWe present the implementation of excited state Born-Oppenheimer molecular dynamics (BOMD) using a polarizable QM/MM approach based on a time-dependent density functional theory (TDDFT) formulation and the AMOEBA force field. The implementation relies on an interface between Tinker and Gaussian software and it uses an algorithm for the calculation of QM/MM energy and forces which scales linearly with the number of MM atoms. The resulting code can perform TDDFT/AMOEBA BOMD simulations on real-life systems with standard computational resources. As a test case, the method is applied to the study of the mechanism of locally-excited to charge-transfer conversion in dimethylaminobenzonitrile in a polar solvent. Our simulations confirm that such a conversion is governed by the twisting of the dimethylamino group which is accompanied by an important reorientation of solvent molecules
A novel coupled-cluster singles and doubles implementation that combines the exploitation of point-group symmetry and Cholesky decomposition of the two-electron integrals
No full textA novel implementation of the coupled-cluster singles and doubles (CCSD) approach is presented that is specifically tailored for the treatment of large symmetric systems. It fully exploits Abelian point-group symmetry and the use of the Cholesky decomposition of the two-electron repulsion integrals. In accordance with modern CCSD algorithms, we propose two alternative strategies for the computation of the so-called particle–particle ladder term. The code is driven toward the optimal choice depending on the available hardware resources. As a large-scale application, we computed the frozen-core correlation energy of buckminsterfullerene (C60) with a polarized valence triple-zeta basis set (240 correlated electrons in 1740 orbitals)
Fast Approximate but Accurate QM/MM Interactions for Polarizable Embedding
No full textThe coupling between the quantum (QM) and classical (MM) regions is often one of the computational bottlenecks when applying polarizable QM/MM to computational spectroscopy. In this Article, we explore three strategies to approximate the QM/MM coupling based on multipole expansion techniques. The implementations of these approximations are benchmarked in terms of both accuracy and computational efficiency and are furthermore applied to the calculation of spectroscopic properties including both one- and two-photon absorption strengths. We show that the proposed strategies provide significant computational savings without compromising the accuracy of the calculated spectroscopic properties
How accurate are EOM-CC4 vertical excitation energies?
No full textWe report the first investigation of the performance of EOM-CC4 - an approximate equation-of-motion coupled-cluster model, which includes iterative quadruple excitations - for vertical excitation energies in molecular systems. By considering a set of 28 excited states in 10 small molecules for which we have computed CC with singles, doubles, triples, quadruples, and pentuples and full configuration interaction reference energies, we show that, in the case of excited states with a dominant contribution from the single excitations, CC4 yields excitation energies with sub-kJ mol-1 accuracy (i.e., error below 0.01 eV), in very close agreement with its more expensive CC with singles, doubles, triples, and quadruples parent. Therefore, if one aims at high accuracy, CC4 stands as a highly competitive approximate method to model molecular excited states, with a significant improvement over both CC3 and CC with singles, doubles, and triples. Our results also evidence that, although the same qualitative conclusions hold, one cannot reach the same level of accuracy for transitions with a dominant contribution from the double excitations
An approximation strategy to compute accurate initial density matrices for repeated self-consistent field calculations at different geometries
No full textRepeated computations on the same molecular system, but with different geometries, are often performed in quantum chemistry, for instance, in ab-initio molecular dynamics simulations or geometry optimisations. While many efficient strategies exist to provide a good guess for the self-consistent field procedure, little is known on how to efficiently exploit the abundance of information generated during the many computations. In this article, we present a strategy to provide an accurate initial guess for the density matrix, expanded in a set of localised basis functions, within the self-consistent field iterations for parametrised Hartree–Fock problems where the nuclear coordinates are changed along with a few user-specified collective variables, such as the molecule's normal modes. Our approach is based on an offline-stage where the Hartree–Fock eigenvalue problem is solved for some particular parameter values and an online-stage where the initial guess is computed very efficiently for any new parameter value. The method allows nonlinear approximations of density matrices, which belong to a non-linear manifold that is isomorphic to the Grassmann manifold, by mapping such a manifold onto the tangent space. Numerical tests on different amino acids show promising initial results
Nonequilibrium Environment Dynamics in a Frequency-Dependent Polarizable Embedding Model
No full textHybrid quantum mechanical/molecular mechanical (QM/MM) models are some of the most powerful and computationally feasible approaches to account for solvent effects or more general environmental perturbations on quantum chemical systems. In their more recent formulations (known as polarizable embedding) they can account for electrostatic and mutual polarization effects between the QM and the MM subsystems. In this paper, a polarizable embedding scheme based on induced dipoles that is able both to describe electron evolution of the embedded QM system in an efficient manner as well as to capture the frequency dependent behavior of the solvent is proposed, namely, ωMMPol. The effects of this frequency-dependent solvent on a time-dependent model system - the Rabi oscillations of H2 + in a resonant field - are considered. The solvent is shown to introduce only mild perturbations when the excitation frequencies of the solvent and the solute are off-resonant. However, the dynamics of the H2 + are fundamentally changed in the presence of a near-resonant excitation solvent. The effectiveness of ωMMPol to simulating realistic chemical systems is demonstrated by capturing charge transfer dynamics within a solvated system
Erratum: “Towards an accurate description of anharmonic infrared spectra in solution within the polarizable continuum model: Reaction field, cavity field and nonequilibrium effects” [J. Chem. Phys. 135, 104505 (2011)]
No full textErratum: “Towards an accurate description of anharmonic infrared
spectra in solution within the polarizable continuum model: Reaction
field, cavity field and nonequilibrium effects” [J. Chem. Phys. 135,
104505 (2011)
A Polarizable CASSCF/MM Approach Using the Interface Between OpenMMPol Library and Cfour
No full textWe present a polarizable embedding quantum mechanics/molecular mechanics (QM/MM) framework for ground- and excited-state Complete Active Space Self-Consistent Field (CASSCF) calculations on molecules within complex environments, such as biological systems. These environments are modeled using the AMOEBA polarizable force field. This approach is implemented by integrating the OpenMMPol library with the CFour quantum chemistry software suite. The implementation supports both single-point energy evaluations and geometry optimizations, facilitated by the availability of analytical gradients. We demonstrate the methodology by applying it to two distinct photoreceptors, exploring the impact of the protein environment on the structural and photophysical properties of their embedded chromophores
Fast Method for Excited-State Dynamics in Complex Systems and Its Application to the Photoactivation of a Blue Light Using Flavin Photoreceptor
No full textThe excited-state dynamics of molecules embedded in complex (bio)matrices is still a challenging goal for quantum chemical models. Hybrid QM/MM models have proven to be an effective strategy, but an optimal combination of accuracy and computational cost still has to be found. Here, we present a method which combines the accuracy of a polarizable embedding QM/MM approach with the computational efficiency of an excited-state self-consistent field method. The newly implemented method is applied to the photoactivation of the blue-light-using flavin (BLUF) domain of the AppA protein. We show that the proton-coupled electron transfer (PCET) process suggested for other BLUF proteins is still valid also for AppA
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