scholarly journals The Halogen-Bond Nature in Noble Gas–Dihalogen Complexes from Scattering Experiments and Ab Initio Calculations

Molecules ◽  
2019 ◽  
Vol 24 (23) ◽  
pp. 4274 ◽  
Author(s):  
Francesca Nunzi ◽  
Benedetta Di Erasmo ◽  
Francesco Tarantelli ◽  
David Cappelletti ◽  
Fernando Pirani
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Halogen Bond ◽  
Noble Gas ◽  
Dynamic Simulations ◽  
Hindered Rotation ◽  
Molecular Beam Scattering ◽  
Definition Of ◽  
High Level ◽  
Selective Formation

In order to clarify the nature of the halogen bond (XB), we considered the prototype noble gas–dihalogen molecule (Ng–X2) systems, focusing on the nature, range, and strength of the interaction. We exploited data gained from molecular beam scattering experiments with the measure of interference effects to obtain a suitable formulation of the interaction potential, with the support of high-level ab initio calculations, and charge displacement analysis. The essential interaction components involved in the Ng–X2 adducts were characterized, pointing at their critical balance in the definition of the XB. Particular emphasis is devoted to the energy stability of the orientational Ng–X2 isomers, the barrier for the X2 hindered rotation, and the influence of the X2 electronic state. The present integrated study returns reliable force fields for molecular dynamic simulations in Ng–X2 complexes that can be extended to systems with increasing complexity and whose properties depend on the selective formation of XB.

scholarly journals The Halogen-Bond Nature in Noble Gas-Dihalogen Complexes from Scattering Experiments and Ab-Initio Calculations

2019 ◽  
Author(s):  
Francesca Nunzi ◽  
Benedetta Di Erasmo ◽  
Francesco Tarantelli ◽  
David Cappelletti ◽  
Fernando Pirani
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Halogen Bond ◽  
Noble Gas ◽  
Hindered Rotation ◽  
Molecular Beam Scattering ◽  
Definition Of ◽  
Dynamics Simulations ◽  
High Level ◽  
Selective Formation

In order to clarify the nature of the halogen bond (XB), we considered the prototype noble gas – dihalogen molecule (Ng-X2) systems, focusing on the nature, range and strength of the interaction. We exploited data gained from molecular beam scattering experiments with the measure of interference effects to obtain a suitable formulation of the interaction potential, with the support of high-level ab initio calculations, and charge displacement analysis. The essential interaction components involved in the Ng-X2 adducts have been characterized, pointing at their critical balance in the definition of the XB. Particular emphasis is devoted to the energy stability of the orientational Ng-X2 isomers, the barrier for the X2 hindered rotation, and the influence of the X2 electronic state. The present integrated study returns reliable force fields for molecular dynamics simulations in Ng-X2 complexes that can be extended to systems with increasing complexity and whose properties depend on the selective formation of XB.

Insight into the halogen-bond nature of noble gas-chlorine systems by molecular beam scattering experiments, ab initio calculations and charge displacement analysis

2019 ◽  
Vol 21 (14) ◽  
pp. 7330-7340 ◽  
Author(s):  
Francesca Nunzi ◽  
Diego Cesario ◽  
Leonardo Belpassi ◽  
Francesco Tarantelli ◽  
Luiz F. Roncaratti ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Molecular Beam ◽  
Halogen Bond ◽  
Noble Gas ◽  
Molecular Beam Scattering ◽  
Beam Scattering ◽  
Charge Displacement ◽  
Insight Into

A weak halogen bond, together with charge transfer from a noble gas to Cl2, characterizes the intermolecular interaction between a noble gas atom and Cl2 in a collinear configuration.

Configurational Assignment and Conformational Study of Methylglyoxal Bisdimethylhydrazones Derived from the 2-Ethoxypropenal Precursor

2006 ◽  
Vol 59 (3) ◽  
pp. 211 ◽  
Author(s):  
Leonid B. Krivdin ◽  
Lyudmila I. Larina ◽  
Kirill A. Chernyshev ◽  
Natalia A. Keiko
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Experimental Measurements ◽  
Conformational Study ◽  
Lone Pairs ◽  
Configurational Assignment ◽  
Out Of Plane ◽  
High Level

A configurational assignment of the isomeric methylglyoxal bisdimethylhydrazones derived from the 2-ethoxypropenal precursor has been performed based on experimental measurements and high-level ab initio calculations of 1J(C,C) and 1J(C,H) couplings. The results reveal the marked stereochemical dependence upon the orientation of the lone pairs of both nitrogen atoms in different isomers. Methylglyoxal bisdimethylhydrazone is shown to exist in a mixture of the EE and ZE isomers (ca. 75:25), both of which adopt predominant s-trans conformations with minor (up to 8°) out-of-plane deviations.

Excitons in poly(para phenylene vinylene): a quantum-chemical perspective based on high-level ab initio calculations

2016 ◽  
Vol 18 (4) ◽  
pp. 2548-2563 ◽  
Author(s):  
Stefanie A. Mewes ◽  
Jan-Michael Mewes ◽  
Andreas Dreuw ◽  
Felix Plasser
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Quantum Chemical ◽  
Phenylene Vinylene ◽  
High Level ◽  
Quantum Chemical Computations

Exciton analyses of high-level quantum-chemical computations for poly(paraphenylene vinylene) reveal the nature of the excitonic bands in PPV oligomers.

scholarly journals Exploration of the NH3–H2 van der Waals interaction by high level ab initio calculations

2008 ◽  
Vol 346 (1-3) ◽  
pp. 237-246 ◽  
Author(s):  
Mirjana Mladenović ◽  
Marius Lewerenz ◽  
Geraldine Cilpa ◽  
Pavel Rosmus ◽  
Gilberte Chambaud
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Van Der Waals ◽  
Van Der Waals Interaction ◽  
High Level

Regular polyhedral molecules. P20 and its inclusion compounds

1998 ◽  
Vol 76 (9) ◽  
pp. 1274-1279 ◽  
Author(s):  
Lubomír Rulísek ◽  
Zdenek Havlas ◽  
Stanislav Hermánek ◽  
Jaromír Plesek
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Inclusion Compounds ◽  
Vibrational Analysis ◽  
Kinetic Stability ◽  
Stabilizing Agents ◽  
Geometrical Properties ◽  
Regular Dodecahedron ◽  
Phosphorus Clusters ◽  
High Level

Based upon the geometrical properties of regular polyhedrons, the possibility of the existence of certain polyhedral molecules composed of only one element is investigated. A very promising candidate - the regular dodecahedron - is selected as the convenient polyhedral structural pattern and phosphorus as the appropriate element. A series of high-level ab initio calculations is performed on the dodecahedral P20 molecule, including predictions of its thermodynamic and kinetic stability, natural bond orbital analysis, vibrational analysis, and inclusion of some elements into the molecular skeleton. Due to the potential stabilizing agents that may eventually form stable inclusion compounds and the estimated high kinetic stability, the question of the possible existence of P20 is answered in the positive.Key words: ab initio calculations, inclusion compounds, P20, phosphorus clusters, polyhedra.

scholarly journals Surface energy of nanoparticles – influence of particle size and structure

2018 ◽  
Vol 9 ◽  
pp. 2265-2276 ◽  
Author(s):  
Dieter Vollath ◽  
Franz Dieter Fischer ◽  
David Holec
Keyword(s):  
Molecular Dynamics ◽  
Particle Size ◽  
Surface Energy ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Molecular Dynamics Simulations ◽  
Definition Of ◽  
Dynamics Simulations ◽  
Classical Thermodynamics ◽  
A Minor

The surface energy, particularly for nanoparticles, is one of the most important quantities in understanding the thermodynamics of particles. Therefore, it is astonishing that there is still great uncertainty about its value. The uncertainty increases if one questions its dependence on particle size. Different approaches, such as classical thermodynamics calculations, molecular dynamics simulations, and ab initio calculations, exist to predict this quantity. Generally, considerations based on classical thermodynamics lead to the prediction of decreasing values of the surface energy with decreasing particle size. This phenomenon is caused by the reduced number of next neighbors of surface atoms with decreasing particle size, a phenomenon that is partly compensated by the reduction of the binding energy between the atoms with decreasing particle size. Furthermore, this compensating effect may be expected by the formation of a disordered or quasi-liquid layer at the surface. The atomistic approach, based either on molecular dynamics simulations or ab initio calculations, generally leads to values with an opposite tendency. However, it is shown that this result is based on an insufficient definition of the particle size. A more realistic definition of the particle size is possible only by a detailed analysis of the electronic structure obtained from initio calculations. Except for minor variations caused by changes in the structure, only a minor dependence of the surface energy on the particle size is found. The main conclusion of this work is that surface energy values for the equivalent bulk materials should be used if detailed data for nanoparticles are not available.

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