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Multiresolution quantum chemistry in multiwavelet bases: excited states from time-dependent Hartree–Fock and density functional theory via linear response

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/C4CP05821F· OSTI ID:1265805
 [1];  [2];  [3];  [4]
  1. Inst. for Molecular Science, Aichi (Japan)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Colorado, Boulder, CO (United States)
  4. Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations

Using the fully numerical method for time-dependent Hartree–Fock and density functional theory (TD-HF/DFT) with the Tamm–Dancoff (TD) approximation we use a multiresolution analysis (MRA) approach to present our findings. From a reformulation with effective use of the density matrix operator, we obtain a general form of the HF/DFT linear response equation in the first quantization formalism. It can be readily rewritten as an integral equation with the bound-state Helmholtz (BSH) kernel for the Green's function. The MRA implementation of the resultant equation permits excited state calculations without virtual orbitals. Moreover, the integral equation is efficiently and adaptively solved using a numerical multiresolution solver with multiwavelet bases. Our implementation of the TD-HF/DFT methods is applied for calculating the excitation energies of H2, Be, N2, H2O, and C2H4 molecules. The numerical errors of the calculated excitation energies converge in proportion to the residuals of the equation in the molecular orbitals and response functions. The energies of the excited states at a variety of length scales ranging from short-range valence excitations to long-range Rydberg-type ones are consistently accurate. It is shown that the multiresolution calculations yield the correct exponential asymptotic tails for the response functions, whereas those computed with Gaussian basis functions are too diffuse or decay too rapidly. Finally, we introduce a simple asymptotic correction to the local spin-density approximation (LSDA) so that in the TDDFT calculations, the excited states are correctly bound.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1265805
Alternate ID(s):
OSTI ID: 1245389
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 47 Vol. 17; ISSN 1463-9076; ISSN PPCPFQ
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (5)

A review on non‐relativistic, fully numerical electronic structure calculations on atoms and diatomic molecules journal May 2019
Magnetic properties with multiwavelets and DFT: the complete basis set limit achieved journal January 2016
Hybrid grid/basis set discretizations of the Schrödinger equation journal December 2017
The any particle molecular orbital grid-based Hartree-Fock (APMO-GBHF) approach journal February 2018
Accurate correlation energies in one-dimensional systems from small system-adapted basis functions journal February 2018

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