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Title: Time-dependent N -electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes

Authors:
 [1];  [1]; ORCiD logo [1];  [1]
  1. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1365432
Grant/Contract Number:
SC0008624; SC0010530
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 24; Related Information: CHORUS Timestamp: 2018-02-14 12:00:02; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Sokolov, Alexander Yu., Guo, Sheng, Ronca, Enrico, and Chan, Garnet Kin-Lic. Time-dependent N -electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes. United States: N. p., 2017. Web. doi:10.1063/1.4986975.
Sokolov, Alexander Yu., Guo, Sheng, Ronca, Enrico, & Chan, Garnet Kin-Lic. Time-dependent N -electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes. United States. doi:10.1063/1.4986975.
Sokolov, Alexander Yu., Guo, Sheng, Ronca, Enrico, and Chan, Garnet Kin-Lic. 2017. "Time-dependent N -electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes". United States. doi:10.1063/1.4986975.
@article{osti_1365432,
title = {Time-dependent N -electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes},
author = {Sokolov, Alexander Yu. and Guo, Sheng and Ronca, Enrico and Chan, Garnet Kin-Lic},
abstractNote = {},
doi = {10.1063/1.4986975},
journal = {Journal of Chemical Physics},
number = 24,
volume = 146,
place = {United States},
year = 2017,
month = 6
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on June 22, 2018
Publisher's Accepted Manuscript

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

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  • A novel approach to strongly contracted N-electron valence perturbation theory (SC-NEVPT2) as a means of describing dynamic electron correlation for quantum chemical density matrix renormalization group (DMRG) calculations is presented. In this approach the strongly contracted perturber functions are projected onto a renormalized Hilbert space. Compared to a straightforward implementation of SC-NEVPT2 with DMRG wavefunctions, the computational scaling and storage requirements are reduced. This favorable scaling opens up the possibility of calculations with larger active spaces. A specially designed renormalization scheme ensures that both the electronic ground state and the perturber functions are well represented in the renormalized Hilbert space.more » Test calculations on the N{sub 2} and [Cu{sub 2}O{sub 2}(en){sub 2}]{sup 2+} demonstrate some key properties of the method and indicate its capabilities.« less
  • Cited by 13
  • New correlation consistent basis sets, cc-pVnZ-PP-F12 (n = D, T, Q), for all the post-d main group elements Ga–Rn have been optimized for use in explicitly correlated F12 calculations. The new sets, which include not only orbital basis sets but also the matching auxiliary sets required for density fitting both conventional and F12 integrals, are designed for correlation of valence sp, as well as the outer-core d electrons. The basis sets are constructed for use with the previously published small-core relativistic pseudopotentials of the Stuttgart-Cologne variety. Benchmark explicitly correlated coupled-cluster singles and doubles with perturbative triples [CCSD(T)-F12b] calculations of themore » spectroscopic properties of numerous diatomic molecules involving 4p, 5p, and 6p elements have been carried out and compared to the analogous conventional CCSD(T) results. In general the F12 results obtained with a n-zeta F12 basis set were comparable to conventional aug-cc-pVxZ-PP or aug-cc-pwCVxZ-PP basis set calculations obtained with x = n + 1 or even x = n + 2. The new sets used in CCSD(T)-F12b calculations are particularly efficient at accurately recovering the large correlation effects of the outer-core d electrons.« less
  • The effect of nanocrystal orientation on the energy loss spectra of monoclinic hafnia (m-HfO{sub 2}) is measured by high resolution transmission electron microscopy (HRTEM) and valence energy loss spectroscopy (VEELS) on high quality samples. For the same momentum-transfer directions, the dielectric properties are also calculated ab initio by time-dependent density-functional theory (TDDFT). Experiments and simulations evidence anisotropy in the dielectric properties of m-HfO{sub 2}, most notably with the direction-dependent oscillator strength of the main bulk plasmon. The anisotropic nature of m-HfO{sub 2} may contribute to the differences among VEELS spectra reported in literature. The good agreement between the complex dielectricmore » permittivity extracted from VEELS with nanometer spatial resolution, TDDFT modeling, and past literature demonstrates that the present HRTEM-VEELS device-oriented methodology is a possible solution to the difficult nanocharacterization challenges given in the International Technology Roadmap for Semiconductors.« less