Ab initio study on (CO2)nclusters via electrostatics‐ and molecular tailoring‐based algorithm

Jose, K. V. Jovan; Gadre, Shridhar R.

doi:10.1002/qua.22110

Cited by 19 publications

(6 citation statements)

References 36 publications

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“…Because of the presence of methyl groups, the structures of neutral acetonitrile clusters exhibit part of the behavior of neutral methanol clusters 32,45‐51 and neutral ethanol clusters, 52‐54 which are stabilized by both hydrogen bonds and CH⋯O interactions. Besides, the dipole–dipole interactions guide the structures of acetonitrile clusters in similar arrangements as those of the carbon dioxide clusters 55‐57 and the nitrous oxide clusters 58‐60 . Oliaee et al 58 observed that the structure of the nitrous oxide tetramer has two highly symmetric isomers, one of which belonging to S 4 symmetry, similar to that of ACN4_1 found in this work.…”

Section: Resultssupporting

confidence: 78%

Binding energies and isomer distribution of neutral acetonitrile clusters

Malloum

Fifen

Conradie

2020

Int J of Quantum Chemistry

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Structures and relative stabilities of neutral acetonitrile clusters up to decamer have been investigated. We used the ABCluster code to thoroughly explore the potential energy surfaces (PESs) of the acetonitrile clusters and to generate initial geometries, which are further fully optimized at the MN15/6-31++G(d,p) level of theory. Our exploration yielded several new local and global minima structures of the acetonitrile clusters. We located new global minimum structures of the acetonitrile pentamer to decamer. The results show that the PESs of the acetonitrile clusters are very flat, yielding several isoenergetic structures. Our investigations also revealed that the stability of the acetonitrile clusters is due both to CHÁ Á ÁN and dipole-dipole interactions. Structures stabilized by the latter are found to be more stable than those stabilized by the former at low temperatures. Furthermore, we examined the effect of temperature on the stability of the structures of the acetonitrile clusters for temperatures in the range 20 to 400 K. We found that several structures contribute to the population of the clusters at high temperatures, and also that a significant contribution to the population comes from isomers that lie within 2.0 kcal/mol from the most stable one. In addition, we used the most stable structures to compute the binding energies of the acetonitrile clusters and to assess the performance of some DFT functionals (MN15, ωB97XD, PW6B95D3, and B2PLYP) in comparison with the MP2 method associated to the aug-cc-pVTZ basis set in calculating the binding energies. We found that the MN15 functional performs better than ωB97XD and PW6B95D3, and that MN15 is less sensitive to the basis set change. We also used an extrapolation scheme to calculate the binding energies of the acetonitrile clusters at the highly accurate W1BD, CBS-QB3, and G4MP2 levels of theory. The resulting binding energies are recommended for future benchmarking of the acetonitrile clusters. K E Y W O R D S acetonitrile clusters, binding energy, DFT functionals, molecular clusters, relative energy, temperature effects, ABCluster code

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Section: Resultssupporting

confidence: 78%

Binding energies and isomer distribution of neutral acetonitrile clusters

Malloum

Fifen

Conradie

2020

Int J of Quantum Chemistry

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“…The EPIC model was also employed for predicting the structures and energetics of a large variety of weakly bonded complexes at negligible computational effort. Jovan Jose and Gadre [ 119 ] investigated the geometric patterns of (CO 2 ) n clusters, with n = 2–8, using the EPIC model for generating energetically favorable initial geometries for subsequent MP2 and DFT-based calculations. The clusters with more C=O…C interactions were found to be associated with higher stabilization energies.…”

Section: Electrostatic Potential For Intermolecular Complexation (Epic) Model and Its Applicationsmentioning

confidence: 99%

Electrostatic Potential Topology for Probing Molecular Structure, Bonding and Reactivity

2021

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Following the pioneering investigations of Bader on the topology of molecular electron density, the topology analysis of its sister field viz. molecular electrostatic potential (MESP) was taken up by the authors’ groups. Through these studies, MESP topology emerged as a powerful tool for exploring molecular bonding and reactivity patterns. The MESP topology features are mapped in terms of its critical points (CPs), such as bond critical points (BCPs), while the minima identify electron-rich locations, such as lone pairs and π-bonds. The gradient paths of MESP vividly bring out the atoms-in-molecule picture of neutral molecules and anions. The MESP-based characterization of a molecule in terms of electron-rich and -deficient regions provides a robust prediction about its interaction with other molecules. This leads to a clear picture of molecular aggregation, hydrogen bonding, lone pair–π interactions, π-conjugation, aromaticity and reaction mechanisms. This review summarizes the contributions of the authors’ groups over the last three decades and those of the other active groups towards understanding chemical bonding, molecular recognition, and reactivity through topology analysis of MESP.

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“…The larger fragment size is difficult to estimate for MTA. The estimate shown in the table is based on data in refs , , and . In MTA, the computational time scales linearly with the system size if the maximum fragment size is held fixed (which is related to the value of R g ).…”

Section: Methods and Principlesmentioning

confidence: 99%

“…Molecular clusters appear to be natural candidates for accurate treatment by fragmentation, because no covalent bonds are broken during the fragmentation process. Thus, from 2008 to the present, Gadre and co-workers have applied their MTA method to clusters of lithium dimers, CO 2 , , benzene, acetylene, , and water . Construction of such clusters and geometry optimization are facilitated by the fragmentation approach. , A fragmentation approach to the description of water clusters, in particular, has been employed by a number of authors. − …”

Section: Historymentioning

confidence: 99%

“…Energy-based molecular fragmentation methods have been applied to such clusters over the last several years, particularly by Gadre and co-workers. These include nonpolar molecules such as Li 2 , CO 2 , , benzene, and acetylene; and polar molecules such as H 2 O, N 2 O, and CH 3 CN. ,,,,,, Reliable calculation of the binding energy in clusters often requires large basis sets and high level ab initio treatment of electron correlation, using methods such as MP2 and CCSD(T), which can be easily employed in conjunction with energy-based fragmentation methods.…”

Section: Applications and Examplesmentioning

confidence: 99%

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