Standard 3D interpolation polynomials often suffer from numerical errors of the calculated field and lack of node points in the 3D solution. We introduce a novel method for accurate and smooth interpolation of arbitrary electromagnetic fields in the vicinity of the optical axis valid up to 90% of the bore radius. Our method combines Fourier analysis and Gaussian wavelet interpolation and provides the axial multipole field functions and their derivatives analytically. The results are accurate and noiseless, usually up to the 5th derivative. This is very advantageous for further applications, such as accurate particle tracing, and evaluation of aberration coefficients and other optical properties. The proposed method also enables studying the strength and orientation of all multipole field components. To illustrate the capabilities of the proposed algorithm, we present three examples: a magnetic lens with a hole in the polepiece, a saturated magnetic lens with an elliptic polepiece, and an electrostatic 8-electrode multipole.
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http://dx.doi.org/10.1016/j.ultramic.2018.03.023 | DOI Listing |
J Chem Inf Model
January 2025
Departments of Molecular Biology and Biochemistry, Chemical and Biomolecular Engineering, Materials Science and Engineering, and Biomedical Engineering, University of California, Irvine, Irvine, California 92697, United States.
Atomic polarizabilities are considered to be fundamental parameters in polarizable molecular mechanical force fields that play pivotal roles in determining model transferability across different electrostatic environments. In an earlier work, the atomic polarizabilities were obtained by fitting them to the B3LYP/aug-cc-pvtz molecular polarizability tensors of mainly small molecules. Taking advantage of the recent PCMRESPPOL method, we refine the atomic polarizabilities for condensed-phase simulations using a polarizable Gaussian Multipole (pGM) force field.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Qingdao Institute for Theoretical and Computational Sciences and Center for Optics Research and Engineering, Shandong University, Qingdao 266237, P. R. China.
A hybrid analytical-numerical integration scheme is introduced to accelerate the Fock build in self-consistent field (SCF) and time-dependent density functional theory (TDDFT) calculations. To evaluate the Coulomb matrix [], the density matrix is first decomposed into two parts, the superposition of atomic density matrices and the rest = -. While [] is evaluated analytically, [] is evaluated fully numerically [with the multipole expansion of the Coulomb potential (MECP)] during the SCF iterations.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
Kenneth S. Pitzer Theory Center and Department of Chemistry, University of California, Berkeley, California 94720, United States.
This work constructs an advanced force field, the Completely Multipolar Model (CMM), to quantitatively reproduce each term of an energy decomposition analysis (EDA) for aqueous solvated alkali metal cations and halide anions and their ion pairings. We find that all individual EDA terms remain well-approximated in the CMM for ion-water and ion-ion interactions, except for polarization, which shows errors due to the partial covalency of ion interactions near their equilibrium. We quantify the onset of the dative bonding regime by examining the change in molecular polarizability and Mayer bond indices as a function of distance, showing that partial covalency manifests by breaking the symmetry of atomic polarizabilities while strongly damping them at short-range.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Aarhus, Denmark.
The minimal basis iterative Stockholder (MBIS) decomposition of molecular electron densities into atomic quantities is an attractive approach for deriving electrostatic parameters in force fields. The MBIS-derived atomic charges, however, in general tend to overestimate the molecular dipole and quadrupole moments by ∼10%. We show that it is possible to derive a constrained MBIS model where the atomic charges or a combination of atomic charges and dipoles exactly reproduce the molecular dipole and quadrupole moments for molecules.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Chemical and Materials Physics Graduate Program, Departments of Molecular Biology and Biochemistry, Chemical and Biomolecular Engineering, Materials Science and Engineering, and Biomedical Engineering, University of California, Irvine, Irvine, California 92697, United States.
Molecular dynamics (MD) simulations are essential for understanding molecular phenomena at the atomic level, with their accuracy largely dependent on both the employed force field and sampling. Polarizable force fields, which incorporate atomic polarization effects, represent a significant advancement in simulation technology. The polarizable Gaussian multipole (pGM) model has been noted for its accurate reproduction of ab initio electrostatic interactions.
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