PMID- 25711489
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20160411
LR  - 20151125
IS  - 1463-9084 (Electronic)
IS  - 1463-9076 (Linking)
VI  - 17
IP  - 47
DP  - 2015 Dec 21
TI  - Multiresolution quantum chemistry in multiwavelet bases: excited states from 
      time-dependent Hartree-Fock and density functional theory via linear response.
PG  - 31405-16
LID - 10.1039/c4cp05821f [doi]
AB  - A fully numerical method for the time-dependent Hartree-Fock and density 
      functional theory (TD-HF/DFT) with the Tamm-Dancoff (TD) approximation is 
      presented in a multiresolution analysis (MRA) approach. 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. 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. 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.
FAU - Yanai, Takeshi
AU  - Yanai T
AD  - Department of Theoretical and Computational Molecular Science, Institute for 
      Molecular Science, Okazaki, Aichi 444-8585, Japan. yanait@ims.ac.jp.
FAU - Fann, George I
AU  - Fann GI
AD  - Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak 
      Ridge, Tennessee 37831, USA.
FAU - Beylkin, Gregory
AU  - Beylkin G
AD  - Department of Applied Mathematics, University of Colorado at Boulder, 526 UCB, 
      Boulder, CO 80309-0526, USA.
FAU - Harrison, Robert J
AU  - Harrison RJ
AD  - Institute for Advanced Computational Science, Stony Brook University, Stony 
      Brook, New York 11794, USA. Robert.Harrison@stonybrook.edu and Computational 
      Science Center, Brookhaven National Laboratory, Upton, New York 11973, USA.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
PT  - Research Support, U.S. Gov't, Non-P.H.S.
PL  - England
TA  - Phys Chem Chem Phys
JT  - Physical chemistry chemical physics : PCCP
JID - 100888160
EDAT- 2015/02/26 06:00
MHDA- 2015/02/26 06:01
CRDT- 2015/02/26 06:00
PHST- 2015/02/26 06:00 [entrez]
PHST- 2015/02/26 06:00 [pubmed]
PHST- 2015/02/26 06:01 [medline]
AID - 10.1039/c4cp05821f [doi]
PST - ppublish
SO  - Phys Chem Chem Phys. 2015 Dec 21;17(47):31405-16. doi: 10.1039/c4cp05821f.