Development of Electron-Proton Density Functionals for Multicomponent Density Functional Theory

Chakraborty, Arindam; Pak, Michael V.; Hammes‐Schiffer, Sharon

doi:10.1103/physrevlett.101.153001

Cited by 103 publications

(75 citation statements)

References 14 publications

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“…These methods have been shown to include sufficient electron-proton correlation to provide accurate nuclear densities. 33,34 Currently these methods are in the development phase and have not yet been applied to systems such as malonaldehyde. …”

Section: Calculation Of Localized Proton Orbitalsmentioning

confidence: 99%

Combining the nuclear-electronic orbital approach with vibronic coupling theory: Calculation of the tunneling splitting for malonaldehyde

Hazra

Skone²,

Hammes‐Schiffer³

2009

The Journal of Chemical Physics

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The nuclear-electronic orbital (NEO) method is combined with vibronic coupling theory to calculate hydrogen tunneling splittings in polyatomic molecules. In this NEO-vibronic coupling approach, the transferring proton and all electrons are treated quantum mechanically at the NEO level, and the other nuclei are treated quantum mechanically using vibronic coupling theory. The dynamics of the molecule are described by a vibronic Hamiltonian in a diabatic basis of two localized nuclear-electronic states for the electrons and transferring proton. This ab initio approach is computationally practical and efficient for relatively large molecules, and the accuracy can be improved systematically. The NEO-vibronic coupling approach is used to calculate the hydrogen tunneling splitting for malonaldehyde. The calculated tunneling splitting of 24.5 cm(-1) is in excellent agreement with the experimental value of 21.6 cm(-1). This approach also enables the identification of the dominant modes coupled to the transferring hydrogen motion and provides insight into their roles in the hydrogen tunneling process.

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Section: Calculation Of Localized Proton Orbitalsmentioning

confidence: 99%

Combining the nuclear-electronic orbital approach with vibronic coupling theory: Calculation of the tunneling splitting for malonaldehyde

Hazra

Skone²,

Hammes‐Schiffer³

2009

The Journal of Chemical Physics

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“…frame, all points of space that satisfy m (1) The inclusion of the c.m. correlations in the exchangecorrelation functional is the major difference with traditional DFT [4,5] and previously developed multicomponent DFT formalisms [8,[16][17][18][19][20], and opens the way to the search for a local c.m. correlations potential, which would a priori be computationally much less costly than the projection techniques used, for instance, in nuclear physics [12,[21][22][23].…”

Section: B Internal Kohn-sham Schemementioning

confidence: 99%

“…Taking into account the quantum nature of the nuclei is important for describing small molecules [14] and solid hydrogen [15], for instance, and explicit treatment of the nuclei is necessary to describe nonadiabatic phenomena. Moreover, taking into account the electron-nuclei correlations can be important for the description of some physical properties [16]. For those reasons, various multicomponent DFT formalisms have been developed [8,[16][17][18][19][20], but in none of them has the c.m.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, taking into account the electron-nuclei correlations can be important for the description of some physical properties [16]. For those reasons, various multicomponent DFT formalisms have been developed [8,[16][17][18][19][20], but in none of them has the c.m. motion been separated properly from the beginning, leading to formal difficulties (that will be detailed in Sec.…”

Section: Introductionmentioning

confidence: 99%

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Generalization of internal density-functional theory and Kohn-Sham scheme to multicomponent self-bound systems, and link with traditional density-functional theory

Messud

2011

Phys. Rev. A

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We generalize the recently developed "internal" density-functional theory (DFT) and Kohn-Sham scheme to multicomponent systems. We obtain a general formalism, applicable for the description of multicomponent self-bound systems (such as molecular systems where the nuclei are treated explicitly, atomic nuclei and mixtures of 3He and 4He droplets), where the fundamental translational symmetry has been treated correctly. The main difference with traditional DFT is the explicit inclusion of center-of-mass correlations in the functional. A large part of the paper is dedicated to the application to molecular systems, which permits us to clarify the approximations that underly traditional DFT

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“…33 Since the nuclearnuclear correlation mostly consists of self-interaction error and the nuclearelectronic correlation originates from a cusp between electrons and nuclei, the most important component of the chemical problems is still electronelectron correlation so Tachikawa and Hammes-Schiffer adopted the electron electron correlation only. 39,54 If we replace the exchange-correlation potential by the HF exchange (or permutation) operator, we can easily obtain a coupled electron and nuclear HF equation. In the latter numerical application, the exchange-correlation energy functional is appropriately treated as HF exchange and the nuclear electronic correlation is neglected for simplicity.…”

Section: Theoretical Development Of Quantum Effects Of Nucleimentioning

confidence: 99%

Molecular Theory Including Quantum Effects and Thermal Fluctuations

Shigeta

2009

Bulletin of the Chemical Society of Japan

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Recent progress in our theoretical developments and applications where thermal fluctuations and quantum effects are important are reviewed. We first show that motions of a confined atom coupled with a fullerene cage cause large thermal fluctuation of the effective charge on the confined atom and that the fluctuation is sensitive to applied temperature and the number of confined species. Second, two different approaches to treat nuclear quantum effects are discussed. One is nonBornOppenheimer (NBO) molecular theory, which is one of an extension of molecular orbital theory for electrons to nuclear motions. This method is suitable to describe static and stationary nuclear (vibrational) states so we apply this method to obtain vibrationally coupled electron density of a protonatable amino acid. We compare the obtained electron density through NBO treatment with conventional calculations. The other approach is referred as to quantum cumulant dynamics (QCD), which is a generalization of quantized Hamiltonian dynamics initially proposed by Prezhdo. This method is applied to vibrational analyses. The ordinary normal mode analysis (NMA) is extended to include quantum degrees of freedom based on QCD formalism, which gives a better description of the vibrational state, where ordinary NMA gives incorrect results. Vibrational frequencies of small molecules by the QCD simulation are compared with those by classical molecular dynamics (MD). It is found that QCD is superior to classical MD in that the results obtained by QCD are in good agreement with those by full quantum treatment. Finally the theoretical background of a real-space gridbased time-dependent density functional theory (RSTDDFT) is explained. This method is applied to solve a NBO problem by using an imaginary time propagator and electron dynamics driven by an off-resonant circularly polarized laser plus in addition to using a real time propagator. For the latter case, we investigate atom-centered dipole moment and induced current and detect the electronic fluctuation in a SiH 4 molecule after irradiation.

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Development of Electron-Proton Density Functionals for Multicomponent Density Functional Theory

Cited by 103 publications

References 14 publications

Combining the nuclear-electronic orbital approach with vibronic coupling theory: Calculation of the tunneling splitting for malonaldehyde

Combining the nuclear-electronic orbital approach with vibronic coupling theory: Calculation of the tunneling splitting for malonaldehyde

Generalization of internal density-functional theory and Kohn-Sham scheme to multicomponent self-bound systems, and link with traditional density-functional theory

Molecular Theory Including Quantum Effects and Thermal Fluctuations

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