Towards an Accurate Model for Halogens in Aqueous Solutions

Bernal-Uruchurtu, Margarita I.; Torres, Adriana Rodríguez; Romero, F. A. Batista; Hernández‐Lamoneda, Ramón

doi:10.1007/978-3-319-21626-3_9

Cited by 2 publications

(3 citation statements)

References 60 publications

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“…For more than a decade now, we have explored different aspects of halogen bonding, in particular, the halogen bond formed between dihalogens, and water molecules motivated by the experiments of the Apkarian and Janda groups 5–8 . Our work has investigated aspects ranging from the most accurate description of the spectroscopic properties 9–11 to the collective effects of halogen in aqueous systems 12–14 . More recently, we have analyzed the performance of different DFA in describing this singular interaction aiming to study the spectroscopic properties of crystalline halogen hydrates systems beyond the single clathrate cage.…”

Section: Introductionmentioning

confidence: 99%

Interaction energy of Cl₂ and Br₂ with H₂O: Exchange, dispersion and density the crucial ingredients

Morera-Boado

Bernal-Uruchurtu

2022

J Comput Chem

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Modern Density Functional Theory models are now suitable for many molecular and condensed phase studies. The study of noncovalent interactions, a well‐known drawback, is no longer an insurmountable obstacle through design and empirical corrections. However, using empirical corrections as in the DFT‐D methods might not be an all‐in‐one solution. This work uses a simple system, X2‐H2O with X = Cl or Br, with two different interactions, halogen‐bonded (XB) and hydrogen‐halogen (HX), to investigate the capability of current density functional approximations (DFA) in predicting interaction energies with eight different exchange‐correlation functionals. SAPT(DFT) provides, for all the studied cases, better predictions than the widely used supermolecular approach. In addition, the components of the interaction energy suggest where some of the shortcomings originate in each DFA. The analysis of the functionals used confirms that PBE0 and ω‐B97X‐D have a physically correct behavior. Using SAPT(DFT) and PBE0, and ω‐B97X‐D, we obtained the interaction energy of Cl2 and Br2 inside different clathrate cages and satisfactorily compared with wavefunction results; hence, the lower and upper limits of this value are defined: Cl2@512, −5.3 ± 0.3 kcal/mol; Cl2@51262, −5.5 ± 0.1 kcal/mol; Br2@51262, −7.6 ± 1.0 kcal/mol; Br2@51263, −10.6 ± 1.0 kcal/mol; Br2@51264, −10.9 ± 0.8 kcal/mol.

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Section: Introductionmentioning

confidence: 99%

Interaction energy of Cl₂ and Br₂ with H₂O: Exchange, dispersion and density the crucial ingredients

Morera-Boado

Bernal-Uruchurtu

2022

J Comput Chem

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“…On the other hand, time-dependent density functional theory (TDDFT) provides efficient access to different states of molecular systems. However, the extent of its applicability rests on the development and validation of approximate exchange-correlation (XC) functionals. , We tested some time ago, as a first approximation, a TDDFT model with the ubiquitous B3LYP functional on small-clusters with disappointing results …”

Section: Introductionmentioning

confidence: 99%

“…24,25 We tested some time ago, as a first approximation, a TDDFT model with the ubiquitous B3LYP functional on small-clusters with disappointing results. 26 In this work, we analyze the description of Br 2 in the tetrakaidecahedral T (5 12 6 2 ), pentakaidecahedral P (5 12 6 3 ), and hexakaidecahedral H (5 12 6 4 ) clathrate cages in the ground and excited states using different DFT methods. One of the goals is classifying the performance of some XC functionals in describing interaction energies, and transition energies to selected excited states of Br 2 inside the clathrate cages.…”

Section: Introductionmentioning

confidence: 99%

Density Functional Study on the Fundamental and Valence Excited States of Dibromine in T, P, and H Clathrate Cages

et al. 2020

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This work evaluates the performance of different DFT models in the accurate prediction of the guest−host intermolecular potentials for the ground and excited states of Br 2 in the tetrakaidecahedral (T), pentakaidecahedral (P), and hexakaidecahedral (H) clathrate cages. Of a set of density functionals, we found that PBE0-D3 and wb97XD provide a physically sound and quantitatively correct description of the interaction and transition energies of low-lying valence excited states of Br 2 inside these clathrate cages. The importance of correctly modeling dispersive interactions is also analyzed. This study provides the first detailed potential energy surface of the ground and excited states of Br 2 in the largest H cage. Comparisons with the LCC2 method and experimental electronic shifts probe the reliability of PBE0-D3 and wb97XD to describe weak intermolecular forces in the ground and excited states.

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Towards an Accurate Model for Halogens in Aqueous Solutions

Cited by 2 publications

References 60 publications

Interaction energy of Cl₂ and Br₂ with H₂O: Exchange, dispersion and density the crucial ingredients

Interaction energy of Cl₂ and Br₂ with H₂O: Exchange, dispersion and density the crucial ingredients

Density Functional Study on the Fundamental and Valence Excited States of Dibromine in T, P, and H Clathrate Cages

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Towards an Accurate Model for Halogens in Aqueous Solutions

Cited by 2 publications

References 60 publications

Interaction energy of Cl2 and Br2 with H2O: Exchange, dispersion and density the crucial ingredients

Interaction energy of Cl2 and Br2 with H2O: Exchange, dispersion and density the crucial ingredients

Density Functional Study on the Fundamental and Valence Excited States of Dibromine in T, P, and H Clathrate Cages

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Interaction energy of Cl₂ and Br₂ with H₂O: Exchange, dispersion and density the crucial ingredients

Interaction energy of Cl₂ and Br₂ with H₂O: Exchange, dispersion and density the crucial ingredients