36 research outputs found
Multiconfigurational Short-Range Density-Functional Theory for Open-Shell Systems
Many chemical systems cannot be described by quantum chemistry methods based
on a singlereference wave function. Accurate predictions of energetic and
spectroscopic properties require a delicate balance between describing the most
important configurations (static correlation) and obtaining dynamical
correlation efficiently. The former is most naturally done through a
multiconfigurational (MC) wave function, whereas the latter can be done by,
e.g., perturbation theory. We have employed a different strategy, namely, a
hybrid between multiconfigurational wave functions and density-functional
theory (DFT) based on range separation. The method is denoted by MC short-range
(sr) DFT and is more efficient than perturbative approaches as it capitalizes
on the efficient treatment of the (short-range) dynamical correlation by DFT
approximations. In turn, the method also improves DFT with standard
approximations through the ability of multiconfigurational wave functions to
recover large parts of the static correlation. Until now, our implementation
was restricted to closed-shell systems, and to lift this restriction, we
present here the generalization of MC-srDFT to open-shell cases. The additional
terms required to treat open-shell systems are derived and implemented in the
DALTON program. This new method for open-shell systems is illustrated on
dioxygen and [Fe(H2O)6]3+.Comment: 37 pages, 3 figures, 4 tables, 1 appendix and 79 references Changes
in v2: 1) Appendix B and reference 81 removed 2) Removed dublicated reference
and corrected reference 31. 3) Added spin-charge cross terms to GGA (Appendix
A). Code changed accordingly and GGA results recalculated. All GGA results
are revised -only small modifications observed. Conclusions are unchange
A quantum-mechanical perspective on linear response theory within polarizable embedding
The derivation of linear response theory within polarizable embedding is
carried out from a rigorous quantum-mechanical treatment of a composite system.
Two different subsystem decompositions (symmetric and nonsymmetric) of the
linear response function are presented, and the pole structures as well as
residues of the individual terms are analyzed and discussed. This theoretical
analysis clarifies which form of the response function to use in polarizable
embedding, and we highlight complications in separating out subsystem
contributions to molecular properties. For example, based on the nonsymmetric
decomposition of the complex linear response function, we derive conservation
laws for integrated absorption cross sections, providing a solid basis for
proper calculations of the intersubsystem intensity borrowing inherent to
coupled subsystems and how that can lead to negative subsystem intensities. We
finally identify steps and approximations required to achieve the transition
from a quantum-mechanical description of the composite system to polarizable
embedding with a classical treatment of the environment, thus providing a
thorough justification for the descriptions used in polarizable embedding
models
Density Matrix Renormalization Group with Efficient Dynamical Electron Correlation Through Range Separation
We present a new hybrid multiconfigurational method based on the concept of
range-separation that combines the density matrix renormalization group
approach with density functional theory. This new method is designed for the
simultaneous description of dynamical and static electron-correlation effects
in multiconfigurational electronic structure problems.Comment: 13 pages, 4 figures, 2 table
Exact two-component Hamiltonians for relativistic quantum chemistry: Two-electron picture-change corrections made simple
Based on self-consistent field (SCF) atomic mean-field (amf) quantities, we present two simple yet computationally efficient and numerically accurate matrix-algebraic approaches to correct both scalar-relativistic and spin–orbit two-electron picture-change effects (PCEs) arising within an exact two-component (X2C) Hamiltonian framework. Both approaches, dubbed amfX2C and e(xtended)amfX2C, allow us to uniquely tailor PCE corrections to mean-field models, viz. Hartree–Fock or Kohn–Sham DFT, in the latter case also avoiding the need for a point-wise calculation of exchange–correlation PCE corrections. We assess the numerical performance of these PCE correction models on spinor energies of group 18 (closed-shell) and group 16 (open-shell) diatomic molecules, achieving a consistent ≈10−5 Hartree accuracy compared to reference four-component data. Additional tests include SCF calculations of molecular properties such as absolute contact density and contact density shifts in copernicium fluoride compounds (CnFn, n = 2,4,6), as well as equation-of-motion coupled-cluster calculations of x-ray core-ionization energies of 5d- and 6d-containing molecules, where we observe an excellent agreement with reference data. To conclude, we are confident that our (e)amfX2C PCE correction models constitute a fundamental milestone toward a universal and reliable relativistic two-component quantum-chemical approach, maintaining the accuracy of the parent four-component one at a fraction of its computational cost
Polarizable embedding with a multiconfiguration short-range density functional theory linear response method
We present here the coupling of a polarizable embedding (PE) model to the recently developed multiconfiguration short-range density functional theory method (MC-srDFT), which can treat multiconfigurational systems with a simultaneous account for dynamical and static correlation effects. PE-MC-srDFT is designed to combine efficient treatment of complicated electronic structures with inclusion of effects from the surrounding environment. The environmental effects encompass classical electrostatic interactions as well as polarization of both the quantum region and the environment. Using response theory, molecular properties such as excitation energies and oscillator strengths can be obtained. The PE-MC-srDFT method and the additional terms required for linear response have been implemented in a development version of DALTON. To benchmark the PE-MC-srDFT approach against the literature data, we have investigated the low-lying electronic excitations of acetone and uracil, both immersed in water solution. The PE-MC-srDFT results are consistent and accurate, both in terms of the calculated solvent shift and, unlike regular PE-MCSCF, also with respect to the individual absolute excitation energies. To demonstrate the capabilities of PE-MC-srDFT, we also investigated the retinylidene Schiff base chromophore embedded in the channelrhodopsin protein. While using a much more compact reference wave function in terms of active space, our PE-MC-srDFT approach yields excitation energies comparable in quality to CASSCF/CASPT2 benchmarks. (C) 2015 AIP Publishing LLC
Molecular quantum mechanical gradients within the polarizable embedding approach—Application to the internal vibrational Stark shift of acetophenone
We present an implementation of analytical quantum mechanical molecular gradients within the
polarizable embedding (PE) model to allow for efficient geometry optimizations and vibrational analysis
of molecules embedded in large, geometrically frozen environments. We consider a variational
ansatz for the quantum region, covering (multiconfigurational) self-consistent-field and Kohn–Sham
density functional theory. As the first application of the implementation, we consider the internal
vibrational Stark effect of the C==O group of acetophenone in different solvents and derive its
vibrational linear Stark tuning rate using harmonic frequencies calculated from analytical gradients
and computed local electric fields. Comparisons to PE calculations employing an enlarged quantum
region as well as to a non-polarizable embedding scheme show that the inclusion of mutual polarization
between acetophenone and water is essential in order to capture the structural modifications and
the associated frequency shifts observed in water. For more apolar solvents, a proper description of
dispersion and exchange–repulsion becomes increasingly important, and the quality of the optimized
structures relies to a larger extent on the quality of the Lennard-Jones parameters