Electron Density Based Partitioning Scheme of Interaction Energies

Mandado, Marcos; Hermida-Ramón, José M.

doi:10.1021/ct100730a

Cited by 44 publications

(44 citation statements)

References 26 publications

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“…There are many schemes for analyzing interaction energies that do not compute a polarization term with the meaning used in this work. The most common approach is to simply treat these two forms of relaxation, polarization and charge transfer, as inseparable, leading to the induction term in the traditional SAPT [5][6][7][8][9] , the orbital term in Bickelhaupt-Baerends EDA [10][11][12] , ETS [13][14][15][16] , and the CI-singles based scheme of Reinhardt et al 17 , as well as the "polarization" term in LMO-EDA [18][19][20] and in the deformation density based scheme of Mandado and Hermida-Ramón 21 .…”

Section: Quantum Mechanical Energiesmentioning

confidence: 99%

Polarization contributions to intermolecular interactions revisited with fragment electric-field response functions

Horn

Head‐Gordon

2015

The Journal of Chemical Physics

113

202

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The polarization energy in intermolecular interactions treated by self-consistent field electronic structure theory is often evaluated using a constraint that the atomic orbital (AO) to molecular orbital transformation is blocked by fragments. This approach is tied to AO basis sets, overestimates polarization energies in the overlapping regime, particularly in large AO basis sets, and lacks a useful complete basis set limit. These problems are addressed by the construction of polarization subspaces based on the responses of isolated fragments to weak electric fields. These subspaces are spanned by fragment electric-field response functions, which can capture effects up to the dipole (D), or quadrupole (DQ) level, or beyond. Schemes are presented for the creation of both non-orthogonal and orthogonal fragment subspaces, and the basis set convergence of the polarization energies computed using these spaces is assessed. Numerical calculations for the water dimer, water-Na(+), water-Mg(2+), water-F(-), and water-Cl(-) show that the non-orthogonal DQ model is very satisfactory, with small differences relative to the orthogonalized model. Additionally, we prove a fundamental difference between the polarization degrees of freedom in the fragment-blocked approaches and in constrained density schemes. Only the former are capable of properly prohibiting charge delocalization during polarization.

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Section: Quantum Mechanical Energiesmentioning

confidence: 99%

Polarization contributions to intermolecular interactions revisited with fragment electric-field response functions

Horn

Head‐Gordon

2015

The Journal of Chemical Physics

113

202

View full text Add to dashboard Cite

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“…In this communication the decomposition of the interaction energy was carried out using the scheme proposed by Mandado and Hermida‐Ramón (density decomposition scheme, DDS), 73 which is based on the partitioning of the one‐electron and exchange‐correlation densities into unperturbed and deformation densities and allows for the representation of the interaction energy as a sum of physically well‐defined electrostatic, exchange, repulsion and polarization terms. In this approach the interaction energy is expressed in terms of the unperturbed densities of the isolated subsystems and the deformation densities, which describe the effect (a) of the Pauli exclusion principle (Δ ρ Pauli ) and (b) of the electron polarization due to the intermolecular interaction (Δ ρ Pol ) on one‐electron densities of monomers.…”

Section: Methodsmentioning

confidence: 99%

Partitioning of the interaction‐induced polarizability of molecules in helium environments

Chołuj

Bartkowiak

2020

Int J of Quantum Chemistry

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In this study, we analyze the correspondence between the spatial confinement represented by the real chemical environment in the form of helium clusters and by the repulsive analytical potential. In doing so, we perform a decomposition of the interaction‐induced polarizability of the LiH and HF molecules in various helium environments into electrostatic, exchange, repulsion and polarization contributions. The obtained results show that in the low and medium orbital compression region the behavior of the repulsion contribution to the interaction‐induced polarizability of LiH and HF embedded in helium environments is in line with the behavior of the total polarizability of molecules entrapped within the repulsive confining potential.

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“…The interaction energy decomposition analysis was performed using an own Fortran code. The interaction energy fragmentation scheme employed in this work is based on the splitting of the one- and two-electron densities into isolated monomers’ densities and interaction terms [38,41]. The interaction energy is decomposed into electrostatic, repulsion, exchange, induction and rest of polarization (mainly dispersion) according to Equation (1) (for details see references [38,41]): EInt=EElec+ERep+EExch+EInd+ERes-Pol…”

Section: Methodsmentioning

confidence: 99%

Potential Application of h-BNC Structures in SERS and SEHRS Spectroscopies: A Theoretical Perspective

Gil‐Guerrero

Otero

Queizán

et al. 2019

Sensors

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In this work, the electronic and optical properties of hybrid boron-nitrogen-carbon structures (h-BNCs) with embedded graphene nanodisks are investigated. Their molecular affinity is explored using pyridine as model system and comparing the results with the corresponding isolated graphene nanodisks. Time-dependent density functional theory (TDDFT) analysis of the electronic excited states was performed in the complexes in order to characterize possible surface and charge transfer resonances in the UV region. Static and dynamic (hyper)polarizabilities were calculated with coupled-perturbed Kohn-Sham theory (CPKS) and the linear and nonlinear optical responses of the complexes were analyzed in detail using laser excitation wavelengths available for (Hyper)Raman experiments and near-to-resonance excitation wavelengths. Enhancement factors around 103 and 108 were found for the polarizability and first order hyperpolarizability, respectively. The quantum chemical simulations performed in this work point out that nanographenes embedded within hybrid h-BNC structures may serve as good platforms for enhancing the (Hyper)Raman activity of organic molecules immobilized on their surfaces and for being employed as substrates in surface enhanced (Hyper)Raman scattering (SERS and SEHRS). Besides the better selectivity and improved signal-to-noise ratio of pristine graphene with respect to metallic surfaces, the confinement of the optical response in these hybrid h-BNC systems leads to strong localized surface resonances in the UV region. Matching these resonances with laser excitation wavelengths would solve the problem of the small enhancement factors reported in Raman experiments using pristine graphene. This may be achieved by tuning the size/shape of the embedded nanographene structure.

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Electron Density Based Partitioning Scheme of Interaction Energies

Cited by 44 publications

References 26 publications

Polarization contributions to intermolecular interactions revisited with fragment electric-field response functions

Polarization contributions to intermolecular interactions revisited with fragment electric-field response functions

Partitioning of the interaction‐induced polarizability of molecules in helium environments

Potential Application of h-BNC Structures in SERS and SEHRS Spectroscopies: A Theoretical Perspective

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