Infrared absorption profiles for small acetonitrile clusters. Theory and experiment

Al-Mubarak, Alaa S.; Mistro, G. Del; Lethbridge, P. G.; Abdul-Sattar, Natik Y.; Stace, A. J.

doi:10.1039/dc9888600209

Cited by 26 publications

(17 citation statements)

References 3 publications

(7 reference statements)

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“…Experimental groups have also worked in understanding the ordering in the structure of both liquid and solid acetonitrile . Some of the studies used both theory and experiment . Most of the studies suggest that acetonitrile prefer an antiparallel dimer structure and bigger clusters consisting of antiparallel dimer units.…”

Section: Introductionmentioning

confidence: 99%

“…[49][50][51][52][53] Some of the studies used both theory and experiment. [54] Most of the studies suggest that acetonitrile prefer an antiparallel dimer structure and bigger clusters consisting of antiparallel dimer units. In this work, our aim is to explore the structural ordering and cooperativity of intermolecular forces in acetonitrile clusters in terms of different types of intermolecular interactions including dipolar and CAHÁÁÁN interactions, pairwise interaction energies, molecular electrostatic potential (MESP), and electron density at intermolecular bond critical points (BCP's) using a density functional (M06L [55] ) which was previously shown [56] to be very good in describing noncovalently interacting systems including acetonitrile dimer.…”

Section: Introductionmentioning

confidence: 99%

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Cooperativity and cluster growth patterns in acetonitrile: A DFT study

Remya

Suresh

2014

J Comput Chem

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Cooperativity in intermolecular interactions and cluster growth patterns of acetonitrile has been studied using M06L density functional theory. Cyclic, ladder-type, stacked, cross-stacked, and mixed patterns are studied. Total interaction energy (E(int)) and interaction energy per monomer (E(m)) show maximum stability and cooperativity in stacked clusters followed by cross-stacked ones. As cluster size increased, magnitude of E(m) showed significant increase. Compared to E(m) of dimer (-2.97 kcal/mol), the increase is 2.6-fold for 27mer. Higher stabilization in larger clusters is attributed to strong cooperativity in intermolecular C-H···N and dipolar interactions. Enhanced cooperativity in stacked structures is supported by atoms-in-molecule electron density (ρ) data. Sum of ρ at intermolecular bond critical points is the highest for stacked clusters. Further, area of negative-valued molecular electrostatic potential is linearly related with E(int) and showed the lowest value in stacked followed by cross-stacked clusters, indicating maximum utilization of lone pair density and maximum cooperativity in such growth patterns. A red shift in the average C-N stretching frequencies with increase in the number of monomers and its direct correlation with E(int) in stacked clusters also supported their stability. Further, two known crystal patterns of acetonitrile (α and β) with 16 monomers are optimized and compared with the most stable hexadecamer pattern and are found to show lower values for E(int) and E(m) compared to the latter. Based on this result, we predict the existence of a third crystal pattern for acetonitrile which will be more ordered and more stable than α and β forms.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cooperativity and cluster growth patterns in acetonitrile: A DFT study

Remya

Suresh

2014

J Comput Chem

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“…42 Acetonitrile clusters have already been the subject of both experimental and theoretical studies. [43][44][45][46][47][48][49][50][51][52][53] Because of the large dipole moment of acetonitrile ͑3.9 D͒, the interactions within these clusters are dominated essentially by dipole-dipole forces, and the lowest energy structures reflect the favorable antiparallel pairing of the molecular dipoles. Molecular dynamics ͑MD͒ and Monte Carlo ͑MC͒ studies have shown that the antiparallel pairing of the dipoles may lead to rigid solidlike structures of the n-even clusters with melting transition temperatures considerably higher than those of the n-odd clusters.…”

Section: Introductionmentioning

confidence: 99%

Experimental and theoretical study of benzene (acetonitrile)n clusters, n=1–4

El‐Shall¹,

Daly²,

Wright³

2002

The Journal of Chemical Physics

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“…Several experimental investigations have been performed to understand the structures of the acetonitrile clusters using different methodologies. Infrared photodissociation spectroscopy was applied to the clusters of acetonitrile 1‐7 . Behrens et al 5 studied the vibrational spectra of the acetonitrile clusters in cold helium droplets and obtained different structures.…”

Section: Introductionmentioning

confidence: 99%

“…Infrared photodissociation spectroscopy was applied to the clusters of acetonitrile. [1][2][3][4][5][6][7] Behrens et al 5 studied the vibrational spectra of the acetonitrile clusters in cold helium droplets and obtained different structures. They found that the spectra from trimers to hexamers are dominated by structures that contain the antiparallel dimer as the building block, with D 2d symmetry for the tetramer.…”

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confidence: 99%

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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Infrared absorption profiles for small acetonitrile clusters. Theory and experiment

Cited by 26 publications

References 3 publications

Cooperativity and cluster growth patterns in acetonitrile: A DFT study

Cooperativity and cluster growth patterns in acetonitrile: A DFT study

Experimental and theoretical study of benzene (acetonitrile)n clusters, n=1–4

Binding energies and isomer distribution of neutral acetonitrile clusters

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