Errors in the numerical solution of the torsion Schr¨odinger equation with Mathieu functions basis set

2019 ◽  
Author(s):  
А.Н. Белов ◽  
В.В. Туровцев ◽  
Ю.Д. Орлов
Keyword(s):  
Fourier Series ◽  
Fourier Expansion ◽  
Continued Fraction ◽  
Basis Set ◽  
Hamiltonian Matrix ◽  
Mathieu Function ◽  
Matrix Elements ◽  
Mathieu Functions ◽  
Expansion Coefficients ◽  
Relative Errors

Рассмотрена погрешность алгоритма аппроксимации функций Матье рядами Фурье, когда коэффициенты ряда Фурье представлены сходящимися цепными дробями. На основании проведенного анализа получены рекуррентные соотношения для абсолютной и относительной погрешностей удерживаемых звеньев цепной дроби и коэффициентов фурье-разложения. Предложен метод оценки точности расчета элементов матрицы гамильтониана торсионного уравнения Шрёдингера в базисе функций Матье. Эффективность предложенного алгоритма подтверждена численными примерами The dependence for the Hamiltonian matrix elements of the Schrodinger torsion equation on the calculation errors of the Mathieu basis set is considered. The Mathieu functions are represented with continued fractions in this study. The analysis of the Mathieu function approximation algorithm using Fourier series expansion is carried out when the coefficients of the Fourier series are represented by convergent continued fractions. It is shown that the major contribution to the errors at the Fourier coefficient calculation is made by the error accumulating in the corresponding elements of the continued fraction. Recurrence relations for the absolute and relative errors of the kept elements of the continued fraction and the Fourier expansion coefficients are obtained. It is shown and illustrated by a numerical example that the absolute and relative errors of the Fourier expansion coefficients in the proposed algorithm are negligible. It is noted that the maximum relative errors of continued fraction are in the highest elements of the kept part. The results of our work are used to estimate the calculation error in the integrals containing Mathieu functions. These integrals constitute the Hamiltonian matrix elements of the Schr¨odinger torsion equation. We developed an algorithm to estimate of the calculation accuracy of the Hamiltonian matrix elements of the Schr¨odinger torsion equation in the basis set of Mathieu functions. We provide the example of this algorithm. The results of the work indicate the adequacy and effectiveness at the application of the Mathieu function basis set to the solution of the Schrdinger torsion equation.¨

Performance of Electronic Structure Methods for the Description of Hückel-Möbius Interconversions in Extended π-Systems

2019 ◽  
Author(s):  
Tatiana Woller ◽  
Ambar Banerjee ◽  
Nitai Sylvetsky ◽  
Xavier Deraet ◽  
Frank De Proft ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Basis Set ◽  
Dft Methods ◽  
Molecular Switching ◽  
Wide Range ◽  
Electronic Structure Methods ◽  
Explicitly Correlated ◽  
Relative Errors ◽  
The Stability ◽  
Basis Set Expansion

<p>Expanded porphyrins provide a versatile route to molecular switching devices due to their ability to shift between several π-conjugation topologies encoding distinct properties. Taking into account its size and huge conformational flexibility, DFT remains the workhorse for modeling such extended macrocycles. Nevertheless, the stability of Hückel and Möbius conformers depends on a complex interplay of different factors, such as hydrogen bonding, p···p stacking, steric effects, ring strain and electron delocalization. As a consequence, the selection of an exchange-correlation functional for describing the energy profile of topological switches is very difficult. For these reasons, we have examined the performance of a variety of wavefunction methods and density functionals for describing the thermochemistry and kinetics of topology interconversions across a wide range of macrocycles. Especially for hexa- and heptaphyrins, the Möbius structures have a pronouncedly stronger degree of static correlation than the Hückel and figure-eight structures, and as a result the relative energies of singly-twisted structures are a challenging test for electronic structure methods. Comparison of limited orbital space full CI calculations with CCSD(T) calculations within the same active spaces shows that post-CCSD(T) correlation contributions to relative energies are very minor. At the same time, relative energies are weakly sensitive to further basis set expansion, as proven by the minor energy differences between MP2/cc-pVDZ and explicitly correlated MP2-F12/cc-pVDZ-F12 calculations. Hence, our CCSD(T) reference values are reasonably well-converged in both 1-particle and n-particle spaces. While conventional MP2 and MP3 yield very poor results, SCS-MP2 and particularly SOS-MP2 and SCS-MP3 agree to better than 1 kcal mol<sup>-1</sup> with the CCSD(T) relative energies. Regarding DFT methods, only M06-2X provides relative errors close to chemical accuracy with a RMSD of 1.2 kcal mol<sup>-1</sup>. While the original DSD-PBEP86 double hybrid performs fairly poorly for these extended p-systems, the errors drop down to 2 kcal mol<sup>-1</sup> for the revised revDSD-PBEP86-NL, again showing that same-spin MP2-like correlation has a detrimental impact on performance like the SOS-MP2 results. </p>

Divergence of Many-Body Perturbation Theory for Noncovalent Interactions of Large Molecules

2019 ◽  
Author(s):  
Brian Nguyen ◽  
Guo P Chen ◽  
Matthew M. Agee ◽  
Asbjörn M. Burow ◽  
Matthew Tang ◽  
...  
Keyword(s):  
Perturbation Theory ◽  
System Size ◽  
State Density ◽  
Second Order ◽  
Binding Energies ◽  
Basis Set ◽  
Many Body ◽  
Many Body Perturbation Theory ◽  
Relative Errors ◽  
Ground State Density

Prompted by recent reports of large errors in noncovalent interaction (NI) energies obtained from many-body perturbation theory (MBPT), we compare the performance of second-order Møller–Plesset MBPT (MP2), spin-scaled MP2, dispersion-corrected semilocal density functional approximations (DFA), and the post-Kohn–Sham random phase approximation (RPA) for predicting binding energies of supramolecular complexes contained in the S66, L7, and S30L benchmarks. All binding energies are extrapolated to the basis set limit, corrected for basis set superposition errors, and compared to reference results of the domain-based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) or better quality. Our results confirm that MP2 severely overestimates binding energies of large complexes, producing relative errors of over 100% for several benchmark compounds. RPA relative errors consistently range between 5-10%, significantly less than reported previously using smaller basis sets, whereas spin-scaled MP2 methods show limitations similar to MP2, albeit less pronounced, and empirically dispersion-corrected DFAs perform almost as well as RPA. Regression analysis reveals a systematic increase of relative MP2 binding energy errors with the system size at a rate of approximately 1‰ per valence electron, whereas the RPA and dispersion-corrected DFA relative errors are virtually independent of the system size. These observations are corroborated by a comparison of computed rotational constants of organic molecules to gas-phase spectroscopy data contained in the ROT34 benchmark. To analyze these results, an asymptotic adiabatic connection symmetry-adapted perturbation theory (AC-SAPT) is developed which uses monomers at full coupling whose ground-state density is constrained to the ground-state density of the complex. Using the fluctuation–dissipation theorem, we obtain a nonperturbative “screened second-order” expression for the dispersion energy in terms of monomer quantities which is exact for non-overlapping subsystems and free of induction terms; a first-order RPA-like approximation to the Hartree, exchange, and correlation kernel recovers the macroscopic Lifshitz limit. The AC-SAPT expansion of the interaction energy is obtained from Taylor expansion of the coupling strength integrand. Explicit expressions for the convergence radius of the AC-SAPT series are derived within RPA and MBPT and numerically evaluated. Whereas the AC-SAPT expansion is always convergent for nondegenerate monomers when RPA is used, it is found to spuriously diverge for second-order MBPT, except for the smallest and least polarizable monomers. The divergence of the AC-SAPT series within MBPT is numerically confirmed within RPA; prior numerical results on the convergence of the SAPT expansion for MBPT methods are revisited and support this conclusion once sufficiently high orders are included. The cause of the failure of MBPT methods for NIs of large systems is missing or incomplete “electrodynamic” screening of the Coulomb interaction due to induced particle–hole pairs between electrons in different monomers, leaving the effective interaction too strong for AC-SAPT to converge. Hence, MBPT cannot be considered reliable for quantitative predictions of NIs, even in moderately polarizable molecules with a few tens of atoms. The failure to accurately account for electrodynamic polarization makes MBPT qualitatively unsuitable for applications such as NIs of nanostructures, macromolecules, and soft materials; more robust non-perturbative approaches such as RPA or coupled cluster methods should be used instead whenever possible.<br>

scholarly journals Analytical angular solutions for the atom–diatom interaction potential in a basis set of products of two spherical harmonics: two approaches

2021 ◽  
Author(s):  
Mariusz Pawlak ◽  
Marcin Stachowiak
Keyword(s):  
Spherical Harmonics ◽  
Interaction Potential ◽  
Chem Phys ◽  
Basis Set ◽  
Matrix Elements ◽  
Trigonometric Functions ◽  
Variational Theory ◽  
Molecular Collision ◽  
The Matrix ◽  
Analytical Expressions

AbstractWe present general analytical expressions for the matrix elements of the atom–diatom interaction potential, expanded in terms of Legendre polynomials, in a basis set of products of two spherical harmonics, especially significant to the recently developed adiabatic variational theory for cold molecular collision experiments [J. Chem. Phys. 143, 074114 (2015); J. Phys. Chem. A 121, 2194 (2017)]. We used two approaches in our studies. The first involves the evaluation of the integral containing trigonometric functions with arbitrary powers. The second approach is based on the theorem of addition of spherical harmonics.

scholarly journals Transient Pressure-Driven Electroosmotic Flow through Elliptic Cross-Sectional Microchannels with Various Eccentricities

Computation ◽  
2021 ◽  
Vol 9 (3) ◽  
pp. 27
Author(s):  
Nattakarn Numpanviwat ◽  
Pearanat Chuchard
Keyword(s):  
Laplace Transform ◽  
Electroosmotic Flow ◽  
Stokes Equations ◽  
Navier Stokes ◽  
Mathieu Functions ◽  
Navier Stokes Equations ◽  
Flow Rates ◽  
Elliptic Cross ◽  
Flow Through ◽  
Relative Errors

The semi-analytical solution for transient electroosmotic flow through elliptic cylindrical microchannels is derived from the Navier-Stokes equations using the Laplace transform. The electroosmotic force expressed by the linearized Poisson-Boltzmann equation is considered the external force in the Navier-Stokes equations. The velocity field solution is obtained in the form of the Mathieu and modified Mathieu functions and it is capable of describing the flow behavior in the system when the boundary condition is either constant or varied. The fluid velocity is calculated numerically using the inverse Laplace transform in order to describe the transient behavior. Moreover, the flow rates and the relative errors on the flow rates are presented to investigate the effect of eccentricity of the elliptic cross-section. The investigation shows that, when the area of the channel cross-sections is fixed, the relative errors are less than 1% if the eccentricity is not greater than 0.5. As a result, an elliptic channel with the eccentricity not greater than 0.5 can be assumed to be circular when the solution is written in the form of trigonometric functions in order to avoid the difficulty in computing the Mathieu and modified Mathieu functions.

Convergence of Breit–Pauli spin–orbit matrix elements with basis set size and configuration interaction space: The halogen atoms F, Cl, and Br

2000 ◽  
Vol 112 (13) ◽  
pp. 5624-5632 ◽  
Author(s):  
Andreas Nicklass ◽  
Kirk A. Peterson ◽  
Andreas Berning ◽  
Hans-Joachim Werner ◽  
Peter J. Knowles
Keyword(s):  
Configuration Interaction ◽  
Interaction Space ◽  
Basis Set ◽  
Spin Orbit ◽  
Matrix Elements ◽  
Set Size ◽  
Halogen Atoms

scholarly journals Spin-Orbit Matrix Elements for a Combined Spin-Flip and IP/EA Approach

2020 ◽  
Author(s):  
Oinam Meitei ◽  
Shannon Houck ◽  
Nicholas Mayhall
Keyword(s):  
Mean Field ◽  
Coupling Constants ◽  
Basis Set ◽  
Reduced Density Matrix ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Matrix Elements ◽  
Dynamical Correlation ◽  
The Core ◽  
Reduced Density

We present a practical approach for computing the Breit-Pauli spin-orbit matrix elements of multiconfigurational systems with both spin and spatial degeneracies based on our recently developed RAS-nSF-IP/EA method (JCTC, 15,<br>2278, 2019). The spin-orbit matrix elements over all the multiplet components are computed using a single one-particle reduced density matrix as a result of the Wigner-Eckart theorem. A mean field spin-orbit approximation was used to account for the two-electron contributions. Basis set dependence as well as the effect of including additional excitations is presented. The effect of correlating the core and semi-core orbitals is also examined. Surprisingly accurate results are obtained for spin-orbit coupling constants, despite the fact that the efficient wavefunction approximations we explore neglect the bulk of dynamical correlation.<br>

A Computationally Efficient Rayleigh–Ritz Model for Heterogeneous Oceanic Waveguides Using Fourier Series of Sound Speed Profile

2021 ◽  
pp. 2150015
Author(s):  
A. D. Chowdhury ◽  
S. K. Bhattacharyya ◽  
C. P. Vendhan
Keyword(s):  
Fourier Series ◽  
Sound Speed ◽  
Transmission Loss ◽  
Ritz Method ◽  
Computational Cost ◽  
Least Square ◽  
Speed Profile ◽  
Matrix Elements ◽  
Sound Speed Profile ◽  
The Matrix

The normal mode method is widely used in ocean acoustic propagation. Usually, finite difference and finite element methods are used in its solution. Recently, a method has been proposed for heterogeneous layered waveguides where the depth eigenproblem is solved using the classical Rayleigh–Ritz approximation. The method has high accuracy for low to high frequency problems. However, the matrices that appear in the eigenvalue problem for radial wavenumbers require numerical integration of the matrix elements since the sound speed and density profiles are numerically defined. In this paper, a technique is proposed to reduce the computational cost of the Rayleigh–Ritz method by expanding the sound speed profile in a Fourier series using nonlinear least square fit so that the integrals of the matrix elements can be computed in closed form. This technique is tested in a variety of problems and found to be sufficiently accurate in obtaining the radial wavenumbers as well as the transmission loss in a waveguide. The computational savings obtained by this approach is remarkable, the improvements being one or two orders of magnitude.

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