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DMRG-CASPT2 study of the longitudinal static second hyperpolarizability of all-trans polyenes

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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
Abstract
We have implemented internally contracted complete active space second order perturbation theory (CASPT2) with the density matrix renormalization group (DMRG) as active space solver [Y. Kurashige and T. Yanai, J. Chem. Phys. 135, 094104 (2011)]. Internally contracted CASPT2 requires to contract the generalized Fock matrix with the 4-particle reduced density matrix (4-RDM) of the reference wavefunction. The required 4-RDM elements can be obtained from 3-particle reduced density matrices (3-RDM) of different wavefunctions, formed by symmetry-conserving single-particle excitations op top of the reference wavefunction. In our spin-adapted DMRG code chemps2 [https://github.com/sebwouters/chemps2], we decompose these excited wavefunctions as spin-adapted matrix product states and calculate their 3-RDM in order to obtain the required contraction of the generalized Fock matrix with the 4-RDM of the reference wavefunction. In this work, we study the longitudinal static second hyperpolarizability of all-trans polyenes C2nH2n+2 [n = 4–12] in the cc-pVDZ basis set. DMRG-SCF and DMRG-CASPT2 yield substantially lower values and scaling with system size compared to RHF and MP2, respectively.
Keywords
complete active space second order perturbation theory, density matrix renormalization group, DENSITY-MATRIX RENORMALIZATION, 2ND-ORDER PERTURBATION-THEORY, NONLINEAR-OPTICAL-PROPERTIES, INITIO QUANTUM-CHEMISTRY, FUNCTIONAL SCHEMES, GROUP ALGORITHM, POLARIZABILITIES, IMPLEMENTATION, CONVERGENCE, FORMULATION

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MLA
Wouters, Sebastian, Veronique Van Speybroeck, and Dimitri Van Neck. “DMRG-CASPT2 Study of the Longitudinal Static Second Hyperpolarizability of All-trans Polyenes.” JOURNAL OF CHEMICAL PHYSICS 145.5 (2016): n. pag. Print.
APA
Wouters, Sebastian, Van Speybroeck, V., & Van Neck, D. (2016). DMRG-CASPT2 study of the longitudinal static second hyperpolarizability of all-trans polyenes. JOURNAL OF CHEMICAL PHYSICS, 145(5).
Chicago author-date
Wouters, Sebastian, Veronique Van Speybroeck, and Dimitri Van Neck. 2016. “DMRG-CASPT2 Study of the Longitudinal Static Second Hyperpolarizability of All-trans Polyenes.” Journal of Chemical Physics 145 (5).
Chicago author-date (all authors)
Wouters, Sebastian, Veronique Van Speybroeck, and Dimitri Van Neck. 2016. “DMRG-CASPT2 Study of the Longitudinal Static Second Hyperpolarizability of All-trans Polyenes.” Journal of Chemical Physics 145 (5).
Vancouver
1.
Wouters S, Van Speybroeck V, Van Neck D. DMRG-CASPT2 study of the longitudinal static second hyperpolarizability of all-trans polyenes. JOURNAL OF CHEMICAL PHYSICS. 2016;145(5).
IEEE
[1]
S. Wouters, V. Van Speybroeck, and D. Van Neck, “DMRG-CASPT2 study of the longitudinal static second hyperpolarizability of all-trans polyenes,” JOURNAL OF CHEMICAL PHYSICS, vol. 145, no. 5, 2016.
@article{8045454,
  abstract     = {We have implemented internally contracted complete active space second order perturbation theory (CASPT2) with the density matrix renormalization group (DMRG) as active space solver [Y. Kurashige and T. Yanai, J. Chem. Phys. 135, 094104 (2011)]. Internally contracted CASPT2 requires to contract the generalized Fock matrix with the 4-particle reduced density matrix (4-RDM) of the reference wavefunction. The required 4-RDM elements can be obtained from 3-particle reduced density matrices (3-RDM) of different wavefunctions, formed by symmetry-conserving single-particle excitations op top of the reference wavefunction. In our spin-adapted DMRG code chemps2 [https://github.com/sebwouters/chemps2], we decompose these excited wavefunctions as spin-adapted matrix product states and calculate their 3-RDM in order to obtain the required contraction of the generalized Fock matrix with the 4-RDM of the reference wavefunction. In this work, we study the longitudinal static second hyperpolarizability of all-trans polyenes C2nH2n+2 [n = 4–12] in the cc-pVDZ basis set. DMRG-SCF and DMRG-CASPT2 yield substantially lower values and scaling with system size compared to RHF and MP2, respectively.},
  articleno    = {054120},
  author       = {Wouters, Sebastian and Van Speybroeck, Veronique and Van Neck, Dimitri},
  issn         = {0021-9606},
  journal      = {JOURNAL OF CHEMICAL PHYSICS},
  keywords     = {complete active space second order perturbation theory,density matrix renormalization group,DENSITY-MATRIX RENORMALIZATION,2ND-ORDER PERTURBATION-THEORY,NONLINEAR-OPTICAL-PROPERTIES,INITIO QUANTUM-CHEMISTRY,FUNCTIONAL SCHEMES,GROUP ALGORITHM,POLARIZABILITIES,IMPLEMENTATION,CONVERGENCE,FORMULATION},
  language     = {eng},
  number       = {5},
  pages        = {9},
  title        = {DMRG-CASPT2 study of the longitudinal static second hyperpolarizability of all-trans polyenes},
  url          = {http://dx.doi.org/10.1063/1.4959817},
  volume       = {145},
  year         = {2016},
}

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