Electron-nucleus correlation functional for multicomponent density-functional theory

Udagawa, Taro; Tsuneda, Takao; Tachikawa, Masanori

doi:10.1103/physreva.89.052519

Cited by 51 publications

(60 citation statements)

References 26 publications

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“…First, we would like to introduce the MC_MO method briefly. More detailed information of MC_MO method is published elsewhere . The total Hamiltonian for a system containing N e ‐electrons, M ‐classical nuclei, and N p ‐quantum nuclei used in MC_MO method is expressed as

H_{t o t} = {140%true \sum}_{i = 1}^{N_{e}} (- \frac{1}{2} \nabla_{i}^{2} - {140%true \sum}_{μ = 1}^{M} \frac{Z_{μ}}{r_{i μ}}) + {140%true \sum}_{i > j}^{N_{e}} \frac{1}{r_{i j}} + {140%true \sum}_{μ > ν}^{M} \frac{Z_{μ} Z_{ν}}{r_{μ ν}} + {140%true \sum}_{p = 1}^{N_{p}} (- \frac{1}{2 M_{p}} \nabla_{p}^{2} + {140%true \sum}_{μ = 1}^{M} \frac{Z_{p} Z_{μ}}{r_{p μ}}) + {140%true \sum}_{p > q}^{N_{p}} \frac{Z_{p} Z_{q}}{r_{p q}} - {140%true \sum}_{i = 1}^{N_{e}} {140%true \sum}_{p = 1}^{N_{p}} \frac{Z_{p}}{r_{i p}},

where the i and j indices refer to the electrons, p and q to the quantum nuclei, μ and ν to the classical nuclei, N e and N p the number of the electrons and quantum nuclei, and M is the number of the classical nuclei.…”

Section: Methodsmentioning

confidence: 99%

“…Conversely, we have recently proposed multicomponent quantum mechanical methods, such as multicomponent molecular orbital (MC_MO) and multicomponent density functional theory (MC_DFT), which can directly take account of the nuclear quantum nature of light particles, such as proton and deuteron. In the MC_MO and MC_DFT schemes, nuclear quantum nature of light particles is directly considered, as well as those of electrons.…”

Section: Introductionmentioning

confidence: 99%

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H/D isotope effect on charge-inverted hydrogen-bonded systems: Systematic classification of three different types in H₃XH^…YH₃(X = C, Si, or Ge, and Y = B, Al, or Ga) with multicomponent calculation

Udagawa

Tachikawa

2015

J. Comput. Chem.

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Three different H/D isotope effect in nine H3 XH(D)···YH3 (X = C, Si, or Ge, and Y = B, Al, or Ga) hydrogen-bonded (HB) systems are classified using MP2 level of multicomponent molecular orbital method, which can take account of the nuclear quantum nature of proton and deuteron. First, in the case of H3 CH(D)···YH3 (Y = B, Al, or Ge) HB systems, the deuterium (D) substitution induces the usual H/D geometrical isotope effect such as the contraction of covalent R(C-H(D)) bonds and the elongation of intermolecular R(H(D)···Y) and R(C···Y) distances. Second, in the case of H3 XH(D)···YH3 (X = Si or Ge, and Y = Al or Ge) HB systems, where H atom is negatively charged called as charge-inverted hydrogen-bonded (CIHB) systems, the D substitution leads to the contraction of intermolecular R(H(D)···Y) and R(X···distances. Finally, in the case of H3 XH(D)···BH3 (X = Si or Ge) HB systems, these intermolecular R(H(D)···Y) and R(X···Y) distances also contract with the D substitution, in which the origin of the contraction is not the same as that in CIHB systems. The H/D isotope effect on interaction energies and spatial distribution of nuclear wavefunctions are also analyzed.

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H_{t o t} = {140%true \sum}_{i = 1}^{N_{e}} (- \frac{1}{2} \nabla_{i}^{2} - {140%true \sum}_{μ = 1}^{M} \frac{Z_{μ}}{r_{i μ}}) + {140%true \sum}_{i > j}^{N_{e}} \frac{1}{r_{i j}} + {140%true \sum}_{μ > ν}^{M} \frac{Z_{μ} Z_{ν}}{r_{μ ν}} + {140%true \sum}_{p = 1}^{N_{p}} (- \frac{1}{2 M_{p}} \nabla_{p}^{2} + {140%true \sum}_{μ = 1}^{M} \frac{Z_{p} Z_{μ}}{r_{p μ}}) + {140%true \sum}_{p > q}^{N_{p}} \frac{Z_{p} Z_{q}}{r_{p q}} - {140%true \sum}_{i = 1}^{N_{e}} {140%true \sum}_{p = 1}^{N_{p}} \frac{Z_{p}}{r_{i p}},

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

H/D isotope effect on charge-inverted hydrogen-bonded systems: Systematic classification of three different types in H₃XH^…YH₃(X = C, Si, or Ge, and Y = B, Al, or Ga) with multicomponent calculation

Udagawa

Tachikawa

2015

J. Comput. Chem.

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“…LDA functionals have been proposed to include the proton–electron and positron‐electron correlation effects in the self‐consistent field (SCF) cycle. We are evaluating the range of applicability of these functionals in molecular systems.…”

Section: Discussionmentioning

confidence: 99%

“…The MC‐DFT approach can be utilized to study NQEs. In these calculations, the exchange‐correlation functional comprises three contributions: the electronic exchange‐correlation functional,

E_{xc}^{e}

, which is usually borrowed from electronic structure DFT; the nuclear exchange‐correlation,

E_{xc}^{n}

, which is neglected since it has been found to be negligible and the nuclear‐electron correlation,

E_{c}^{en}

, for which local density approximation (LDA) functionals have been proposed . Still, in some applications of APMO‐DFT, the nuclear‐electronic correlation has been neglected …”

Section: Apmo Wavefunction Methodsmentioning

confidence: 99%

The any particle molecular orbital approach: A short review of the theory and applications

Reyes

Moncada

Charry

2018

Int J of Quantum Chemistry

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The any particle molecular orbital (APMO) approach extends regular electronic structure methods to study atomic and molecular systems in which electrons and other particles are treated simultaneously as quantum waves. A number of electronic structure methodologies have been extended under the APMO framework and applied to investigate nuclear quantum effects including isotope effects and nuclear delocalization and to calculate proton binding energies and affinities. In addition, APMO methodologies have been employed to analyze physical and chemical properties of atomic and molecular systems containing exotic subatomic particles.

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“…Nuclei are treated as classical point charges in the conventional QM methods, and the NQE is not directly taken into account. On the other hand, we have recently developed the multicomponent QM (MC_QM) methods to directly consider the NQE of light particles, such as proton and deuteron. In the MC_QM treatment, light nuclei are treated as quantum wavefunction as well as electrons.…”

Section: Introductionmentioning

confidence: 99%

Multicomponent QM study on the reaction of HOSO + NO₂ with H₂O: Nuclear quantum effect on structure and reaction energy profile

Sugimoto

Tachikawa

Udagawa

2018

Int J of Quantum Chemistry

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The hydrogen transfer reaction in the reaction of HOSO + NO2 with and without H2O have been investigated using multicomponent quantum‐mechanics method, which can directly take nuclear quantum effect (NQE) of light nuclei into account. For the case of the reaction without H2O, our calculation reveals that the reaction leading to trans‐HONO is preferred. For the reaction with H2O, water‐non‐mediated and water‐mediated (hydrogen‐relay) hydrogen transfer mechanism are investigated. The NQE of hydrogen nucleus lowers the relative energy of the stationary point structures and reduces the activation barrier of the reactions. The largest stabilization is found in the transition state structure of the hydrogen‐relay type reaction. H/D isotope effects for the reactions are also analyzed. In particular, H/D isotope effect on the activation barrier is analyzed in detail with the aid of the active strain model.

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Electron-nucleus correlation functional for multicomponent density-functional theory

Cited by 51 publications

References 26 publications

H/D isotope effect on charge-inverted hydrogen-bonded systems: Systematic classification of three different types in H₃XH^…YH₃(X = C, Si, or Ge, and Y = B, Al, or Ga) with multicomponent calculation

H/D isotope effect on charge-inverted hydrogen-bonded systems: Systematic classification of three different types in H₃XH^…YH₃(X = C, Si, or Ge, and Y = B, Al, or Ga) with multicomponent calculation

The any particle molecular orbital approach: A short review of the theory and applications

Multicomponent QM study on the reaction of HOSO + NO₂ with H₂O: Nuclear quantum effect on structure and reaction energy profile

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Electron-nucleus correlation functional for multicomponent density-functional theory

Cited by 51 publications

References 26 publications

H/D isotope effect on charge-inverted hydrogen-bonded systems: Systematic classification of three different types in H3XH…YH3(X = C, Si, or Ge, and Y = B, Al, or Ga) with multicomponent calculation

H/D isotope effect on charge-inverted hydrogen-bonded systems: Systematic classification of three different types in H3XH…YH3(X = C, Si, or Ge, and Y = B, Al, or Ga) with multicomponent calculation

The any particle molecular orbital approach: A short review of the theory and applications

Multicomponent QM study on the reaction of HOSO + NO2 with H2O: Nuclear quantum effect on structure and reaction energy profile

Contact Info

Product

Resources

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H/D isotope effect on charge-inverted hydrogen-bonded systems: Systematic classification of three different types in H₃XH^…YH₃(X = C, Si, or Ge, and Y = B, Al, or Ga) with multicomponent calculation

H/D isotope effect on charge-inverted hydrogen-bonded systems: Systematic classification of three different types in H₃XH^…YH₃(X = C, Si, or Ge, and Y = B, Al, or Ga) with multicomponent calculation

Multicomponent QM study on the reaction of HOSO + NO₂ with H₂O: Nuclear quantum effect on structure and reaction energy profile