Über eine Näherung zur Lösung des “Self-consistent-field” Verfahrens für Systeme mit ungepaarten Elektronen I. Die Methode

An approximate solution of the SCF problem for systems with unpaired electrons (open-shell) is proposed. The equations are given and the results are discussed.     

Effective potential theory of atom–diatom scattering in the presence of “intermediate” reactive channels

A field-theoretical formalism is applied to the problem of atom–diatom scattering, in the presence of “intermediate” reactive channels. This leads to an integral equation formulation for elastic processes and to a numerical quadrature problem for inelastic vibro–rotational transitions. The key quantity of the theory is represented by an effective potential that contains full information on the dynamics of the process. A closed equation is obtained for this quantity, along with an approximation scheme of the second order in the system interaction potential. A diagrammatic technique is introduced and the physical interpretation of the approximate form of the effective potential considered.     

Scaled one-electron hamiltonian model for open-shell LCAO–MO–SCF calculations: Comparison with the restricted open-shell method of roothaan

The performance of a recently proposed scaled one-electron Hamiltonian (SOEH ) model is tested against parallel sets of restricted open-shell calculations by the method of Roothaan. It is found that the energy calculated by SOEH model, in general, lies slightly higher than the energy computed by the restricted open-shell method of Roothaan lending credibility to the application of variational argument to the scaled pseudoenergy functional (E^av) for deriving the SOEH model. The numerical stability of the converged SOEH energy with respect to changes in trial vectors indicates the reliability of the method. The SOEH model is shown to perform well in the calculation of geometries of radicals and ions. The convergence behavior of the SOEH model is compared with that of the restricted open-shell method of Roothaan.     

Long-range excitations in time-dependent density functional theory

Adiabatic time-dependent density functional theory fails for excitations of a heteroatomic molecule composed of two open-shell fragments at large separation. Strong frequency dependence of the exchange-correlation kernel is necessary for both local and charge-transfer excitations. The root of this is the static correlation created by the step in the exact Kohn-Sham ground-state potential between the two fragments. An approximate nonempirical kernel is derived for excited molecular dissociation curves at large separation. Our result is also relevant when the usual local and semilocal approximations are used for the ground-state potential, as static correlation there arises from the coalescence of the highest occupied and lowest unoccupied orbital energies as the molecule dissociates.     

Theoretical Study on Divergence Problems of Single Reference Perturbation Theories

Divergences of the single reference perturbation theories due to the addition of diffusion basis functions have been investigated for both closed-shell and open-shell molecular systems. It is found that the oscillatory range of perturbation energies of open-shell systems increases as the spin multiplicity of systems changes from 2 to 4. Feenberg transformation is exploited to treat the divergence problems. It is found numerically that within the interval of Feenberg parameter there exists a minimum perturbation order at which the perturbation series become convergent. It is also found for the open-shell systems that the magnitude of the corresponding Feenberg parameter becomes larger as the spin multiplicity of the system of interest changes from 2 to 4.     

Spin-adapted open-shell time-dependent density functional theory. III. An even better and simpler formulation

The recently proposed spin-adapted time-dependent density functional theory (S-TD-DFT) [Z. Li and W. Liu, J. Chem. Phys. 133, 064106 (2010)] resolves the spin-contamination problem in describing singly excited states of high spin open-shell systems. It is an extension of the standard restricted open-shell Kohn-Sham-based TD-DFT which can only access those excited states due to singlet-coupled single excitations. It is also far superior over the unrestricted Kohn-Sham-based TD-DFT (U-TD-DFT) which suffers from severe spin contamination for those excited states due to triplet-coupled single excitations. Nonetheless, the accuracy of S-TD-DFT for high spin open-shell systems is still inferior to TD-DFT for well-behaved closed-shell systems. The reason can be traced back to the violation of the spin degeneracy conditions (SDC) by approximate exchange-correlation (XC) functionals. Noticing that spin-adapted random phase approximation (S-RPA) can indeed maintain the SDC by virtue of the Wigner-Eckart theorem, a hybrid ansatz combining the good of S-TD-DFT and S-RPA can immediately be envisaged. The resulting formalism, dubbed as X-TD-DFT, is free of spin contamination and can also be viewed as a S-RPA correction to the XC kernel of U-TD-DFT. Compared with S-TD-DFT, X-TD-DFT leads to much improved results for the low-lying excited states of, e.g., N(2)(+), yet with much reduced computational cost. Therefore, X-TD-DFT can be recommended for routine calculations of excited states of high spin open-shell systems.     

Wilson–Sommerfeld quantization rule revisited

A fresh look at the origin of the Wilson–Sommerfeld quantization rule has been pursued to gain new insight. The rule is shown to provide states that satisfy several well‐known theorems of standard quantum mechanics. A few other useful results and scaling relations are also derived. They emerge to act as nice guiding rules of thumb in the course of rigorous computations. Certain features of true excited‐state densities can be understood. Goodness of approximate densities can be assessed. Compressed systems can be studied profitably. A route is also sketched that allows one to retrieve classical trajectories from near‐exact energy eigenfunctions for both bound and resonant states by exploiting this rule. Additionally, a discussion on semiclassical perturbation theory is presented emphasizing the asymptotic behavior. Pilot calculations demonstrate the success of the present endeavor under various circumstances. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 113–125, 2001     

Direct minimization of the energy functional in LCAO–MO calculations

In this paper we obtain formulae useful in methods for the direct minimization of the energy functional in the LCAO -MO -MC -SCF approach. The formulae are appropriate for dealing with variations in both the linear and nonlinear parameters. We include formulae for the usual closed- and open-shell problems as special cases.     

Lower scaling approximation to EOM‐CCSD: A critical assessment of the ionization problem

In this article, we investigate the performance of different approximate variants of the EOM‐CCSD method for calculation of ionization potential (IP), as compared to EOM‐CCSDT reference values. None of the lower scaling approximations to the EOM‐CCSD method give a consistent performance for valence, inner valence, and core ionization, favoring one, or the other depending on the nature of the approximation used. The parent EOMIP‐CCSD method gives superior performance for valence IP but can show large errors for inner valence and core ionization. The problem is particularly severe for core‐ionization, where even the EOMIP‐CCSDT method cannot provide quantitative accuracy.     

Feenberg scaling and higher-order invariants in Rayleigh–Schrödinger perturbation theory

It is shown that the determination of a unique scaling parameter, based on scale-invariant forms for energy in the scaled zero-order Hamiltonian approach of Feenberg, is not possible because the higher-order invariants themselves are nonunique.     

Approximation of enzyme kinetics for high enzyme concentration by a first order perturbation approach

This contribution presents an approximate solution of the enzyme kinetics problem for the case of excess of an enzyme over the substrate. A first order perturbation approach is adopted where the perturbation parameter is the relation of the substrate concentration to the total amount of enzyme. As a generalization over existing solutions for the same problem, the presented approximation allows for nonzero initial conditions for the substrate and the enzyme concentrations as well as for nonzero initial complex concentration. Nevertheless, the approximate solution is obtained in analytical form involving only elementary functions like exponentials and logarithms. The presentation discusses all steps of the procedure, starting from amplitude and time scaling for a non-dimensional representation and for the identification of the perturbation parameter. Suitable time constants lead to the short term and long term behaviour, also known as the inner and outer solution. Special attention is paid to the matching process by the definition of a suitable intermediate layer. The results are presented in concise form as a summary of the required calculations. An extended example compares the zero order and first order perturbation approximations for the short term and long term solution as well as the uniform solution. A comparison to the numerical solution of the initial set of nonlinear ordinary differential equations demonstrates the achievable accuracy.     

On the degeneracy of atomic states within exact-exchange (spin-) density functional theory

The problem of degenerate ground states of open-shell atoms is investigated in spin-restricted and spin-unrestricted density functional theories using the exact-exchange energy functional. For the spin-unrestricted case, spurious energy splittings of the order of 2-3 kcal/mol are found for atoms of the second and third periods which are larger than the splittings obtained from recently proposed approximate exchange functionals depending explicitly on the current density. In remarkable contrast, for spin-restricted calculations the degeneracy of different atomic ground states is recovered to within less than 0.6 kcal/mol.     

Some aspects of the model potential method

The theoretical justification of the model potential method is studied in some detail. The correct equations within the framework of Roothaan's open-shell scheme are derived and the approximations necessary to get a workable method are discussed. Analysis of the local part of the model potential suggests a new analytical form for it. The new expression is theoretically more consistent than the original one, and it can be determined in a more straightforward way. A basis set approximation, which is particularly suitable for approximate evaluation of two-electron integrals when only valence orbitals are involved, is discussed and tested with encouraging results. The ideas are tested on the Fe and I atoms.     

Spin-Adapted restricted Hartree–Fock reference coupled-cluster theory for open-shell systems: Noniterative triples for noncanonical orbitals

The coupled clusters singles and doubles (CCSD ) method for calculations of open-shell systems with the single restricted Hartree–Fock (ROHF ) reference determinant is extended by the noniterative triples to give CCSD(T) . Our approach profits from the fact that (a) single- and double-excitation amplitudes are spin-adapted, which directly leads to a computationally less demanding algorithm than are nonadapted procedures and produces the spin-adapted CCSD wave function and (b) triple excitations calculated from converged spin-adapted (SA ) CCSD amplitudes are also obtained more effectively. Altogether, computer demands of our SA CCSD(T) approach, applicable to high-spin open-shell cases which are well represented by a single-determinant reference is comparable to that for closed-shell systems. Our approach is not based on semicanonical orbitals, applied by Bartlett's group. However, we compare some other possible choices of ROHF orbitals to this “standard.” Numerical results for a series of atoms and molecules demonstrate little sensitivity to this selection. © 1995 John Wiley & Sons, Inc.     

Addendum to “variational principle for obtaining approximate analytical solutions of the temperature-perturbed Thomas–Fermi equation for compressed atoms”

In the present work the total energy of a Ne atom at T = 0 K is calculated as a function of a spherical container radius. The calculation is based on the Thomas–Fermi (TF ) equation, which is solved approximately by an equivalent variational principle. The effect of an approximate exchange correction on the variational TF energy values is investigated.     

Numerical method for the open-shell restricted hartree–fock density-matrix direct calculation

A new computation procedure for direct calculation of the density matrix in the LCAO version of the restricted Hartree–Fock–Roothaan open-shell theory is analyzed. It is proved that the procedure is quadratically convergent and stable to the round-off errors independently of the Fock operator spectrum. The dependence of the limit matrix of the initial matrix is examined.     

(Hyper)polarizability density analysis for open-shell molecular systems based on natural orbitals and occupation numbers

We have developed a method for analyzing the (hyper)polarizabilities of open-shell molecular systems. This method employs the (hyper)polarizability densities based on the natural orbitals and occupation numbers, which enables us to analyze the contributions of odd electrons having various open-shell (diradical) characters. Within broken-symmetry, i.e., spin-unrestricted, single-determinant molecular orbital and density functional theory approaches, we can also remove the spin contamination effects on these quantities through spin projection. To do that, an approximate spin projected method has been elaborated and applied to the analysis of the (hyper)polarizability of multi-radical systems. As examples, typical open-shell singlet systems, 1,3-dipoles and rectangular graphene nanoflakes, are examined.     

Scattering in view of the Titchmarsh–Weyl theory

The Titchmarsh–Weyl theory for a singular second-order differential equation is presented. The equations, however, are arranged such that the theory is immediately applicable to the multichannel formulation. The mathematical basis of the Titchmarsh–Weyl theory (TWT) is outlined and the Titchmarsh–Weyl m function is presented. Relations to the associated Green's function and the spectral function are given. It is shown how some quantities common in scattering theory can be expressed in terms of the TWT. The method of complex rotation is then applied to the TWT to create a complex rotated analog of the Titchmarsh–Weyl theory. This is then extended as exterior complex scaling is introduced. An outline of a proof for the method of exterior complex scaling is presented and some numerical results of the complete theory are given.     

Flexible ligand docking without parameter adjustment across four ligand–receptor complexes

Understanding molecular recognition is one of the fundamental problems in molecular biology. Computationally, molecular recognition is formulated as a docking problem. Ideally, a molecular docking algorithm should be computationally efficient, provide reasonably thorough search of conformational space, obtain solutions with reasonable consistency, and not require parameter adjustments. With these goals in mind, we developed DIVALI (Docking wIth eVolutionary AlgorIthms), a program which efficiently and reliably searches for the possible binding modes of a ligand within a fixed receptor. We use an AMBER-type potential function and search for good ligand conformations using a genetic algorithm (GA). We apply our system to study the docking of both rigid and flexible ligands in four different complexes. Our results indicate that it is possible to find diverse binding modes, including structures like the crystal structure, all with comparable potential function values. To achieve this, certain modifications to the standard GA recipe are essential. © 1995 John Wiley & Sons, Inc.     

Hierarchical atom type definitions and extensible all‐atom force fields

The extensibility of force field is a key to solve the missing parameter problem commonly found in force field applications. The extensibility of conventional force fields is traditionally managed in the parameterization procedure, which becomes impractical as the coverage of the force field increases above a threshold. A hierarchical atom‐type definition (HAD) scheme is proposed to make extensible atom type definitions, which ensures that the force field developed based on the definitions are extensible. To demonstrate how HAD works and to prepare a foundation for future developments, two general force fields based on AMBER and DFF functional forms are parameterized for common organic molecules. The force field parameters are derived from the same set of quantum mechanical data and experimental liquid data using an automated parameterization tool, and validated by calculating molecular and liquid properties. The hydration free energies are calculated successfully by introducing a polarization scaling factor to the dispersion term between the solvent and solute molecules. © 2015 Wiley Periodicals, Inc.