Molecular (global) and atom-in-cluster (local) polarizabilities of medium-size gold nanoclusters: isomer structure effects

Rodríguez, Juan I.; Baltazar-Méndez, María I.; Autschbach, Jochen; Castillo-Alvarado, F. L.

doi:10.1140/epjd/e2013-30570-3

Cited by 5 publications

(5 citation statements)

References 40 publications

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“…Figure shows the gold cluster complex Au 4 −S−C 6 H 4 −S′−Au′ 4 , which is composed of a benzene ring linking two gold nanoclusters Au 4 through sulfur atoms . The nature of the sulfur–gold and gold–gold chemical bonds in these types of complexes was previously analyzed in detail by us using ZORA‐QTAIM . Thus, we focus here only on the new features on the QTAIM topology (chemical bonding) in these gold complex systems due to relativistic effects.…”

Section: Resultsmentioning

confidence: 99%

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Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

Anderson

Rodríguez

Ayers

et al. 2019

Chemistry A European J

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The topology of the molecular electron density of benzene dithiol gold cluster complex Au4−S−C6H4−S′−Au′4 changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.

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Section: Resultsmentioning

confidence: 99%

“…Both singlet and triplet spin multiplicities were considered. QTAIM topology and properties were determined by an unrestricted single‐point (SP) calculation at the optimized geometry using the QTAIM module in ADF …”

Section: Computational Detailsmentioning

confidence: 99%

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

Anderson

Rodríguez

Ayers

et al. 2019

Chemistry A European J

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“…First of all, notice that the eqs. and are satisfied to accepted numerical precision (

L_{Ω}

∼10 −3 ), which is the standard accepted accuracy of our high performance QTAIM method implemented in ADF for nonrelativistic computations . This accuracy in the integration of the Laplacian is sufficient for obtaining QTAIM property values (charge, dipole moments, polarizability, etc.)…”

Section: Resultsmentioning

confidence: 72%

“…with the accuracy of standard QTAIM codes (see Refs. ). So our numerical implementation correctly confirms the result of Anderson and Ayers, which states that integration of the Laplacian of the electron density over any atomic volume is equal to zero in the relativistic SR‐ZORA case [see eq.…”

Section: Resultsmentioning

confidence: 97%

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Relativistic (SR‐ZORA) quantum theory of atoms in molecules properties

et al. 2016

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The Quantum Theory of Atoms in Molecules (QTAIM) is used to elucidate the effects of relativity on chemical systems. To do this, molecules are studied using density-functional theory at both the nonrelativistic level and using the scalar relativistic zeroth-order regular approximation. Relativistic effects on the QTAIM properties and topology of the electron density can be significant for chemical systems with heavy atoms. It is important, therefore, to use the appropriate relativistic treatment of QTAIM (Anderson and Ayers, J. Phys. Chem. 2009, 115, 13001) when treating systems with heavy atoms. © 2016 Wiley Periodicals, Inc.

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Exploring the nature of the interactions between the molecules of the sodium dodecyl sulfate and water in crystal phases and in the water/vacuum interface

Aray

Parra

Paredes

et al. 2020

Heliyon

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The nature of the interaction between the molecules of the sodium dodecyl sulfate surfactant forming two crystal phases, one anhydrous, NaC 12 H 25 O 4 S and the other, NaC 12 H 25 O 4 S.H 2 O, hydrated with one water molecule for unit cell, has been studied in detail using the quantum theory of atoms in molecules and a localized electron detector function. It was found that for the anhydrous crystal, the head groups of the surfactant molecules are linked into a head-to-head pattern, by a bond path network of Na-O ionic bonds, where each Na þ atom is attached to four SO À 4 groups. For the hydrated crystal, in addition to these four bonds for Naþ, two additional ones appear with the oxygen atoms of the water molecules, forming a bond paths network of ionic Na-O bonds, that link the Na þ atoms with the SO À 4 groups and the H 2 O molecules. Each H 2 O molecule is bonded to two SO À 4 groups via hydrogen bonds, while the SO À 4 groups are linked to a maximum of four Naþ atoms. The phenomenon of aggregation of the sodium dodecyl sulfate molecules at the liquid water/vacuum interface was studied using NVT molecular dynamics simulations. We have found that for surfactant aggregates, the Naþ ions are linked to a maximum of three SO 4 groups and three water molecules that form Na-O bonds. Unlike hydrated crystal, each of the O atoms that make these Na-O bonds is linked to only one Naþ ion. Despite these differences, like the crystal phases, the surfactant molecules tend to form a head-to-head network pattern of ionic Na-O bonds that link their heads. The present results indicate that the clustering of anionic surfactant at the water/vacuum interface is a consequence of the electrostatic alignment of the cationic and anionic groups as occurs in the crystalline phases of sodium dodecyl sulfate.

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Molecular (global) and atom-in-cluster (local) polarizabilities of medium-size gold nanoclusters: isomer structure effects

Cited by 5 publications

References 40 publications

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

Relativistic (SR‐ZORA) quantum theory of atoms in molecules properties

Exploring the nature of the interactions between the molecules of the sodium dodecyl sulfate and water in crystal phases and in the water/vacuum interface

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