Intermolecular orientations in liquid acetonitrile: New insights based on diffraction measurements and all-atom simulations

Abstract

Intermolecular correlations in liquid acetonitrile (CH 3 CN) have been revisited by calculating orientational correlation functions. In the present approach, hydrogen atoms are included, so that a concept applicable for molecules of (nearly) tetrahedral shape can be exploited. In this way molecular arrangements are elucidated not only for closest neighbours but also extending well beyond the first coordination sphere. Thus a complementary viewpoint is provided to the more popular dipole-dipole correlations. Our calculations are based on large structural models that were obtained by applying diffraction data and partial radial distribution functions from potential-based (all-atom) molecular dynamics simulation simultaneously, within the framework of the Reverse Monte Carlo method.

Spin-state dependence of the structural and vibrational properties of solvated iron(ii) polypyridyl complexes from AIMD simulations: III. [Fe(tpen)]Cl2 in acetonitrile

“…The similarity between the RDFs determined for the complex in the two states indicate that the structure of the ACN solvent is not signicantly affected by the change of spin states. The calculated RDFs are in very good agreement with those determined for liquid ACN from X-ray and neutron diffraction data by Pothoczki and Puszta using the reverse Monte Carlo method, 86 The C 1 ACN -C 1 ACN , C 1 ACN -N, N ACN -H ACN , N ACN -N ACN RDFs are also in very good agreement with those recently determined for liquid ACN by Sánchez Marcos and coworkers from MD simulations performed using the exible and polarizable force eld which they designed for the accurate description of ACN in the solid, liquid and gas phases. 87 Consequently, the present AIMD simulations allowed to achieve an accurate characterization of the ACN solvent for the [Fe(tpen)]Cl 2 solution in the two spin states.…”

Local order in binary Ge-Te glasses – An experimental study

“…This method is widely used to study the structure of liquids and glasses (see e.g. [16,17]). The uncertainty of short range order parameters is also investigated.…”

Solvation of anthraquinone and Tempo redox-active species in acetonitrile using a polarizable force field

“…Bottom panel: comparison between the X-ray structure factor as obtained by experiment and calculated using the FF. 39 Exp Other properties of liquid acetonitrile (namely heat of vaporization, dielectric constant, diffusion coefficient and viscosity) were also computed. They are summarized in Table S7 in the SI and compared to the respective values obtained with force fields from the literature 33,34,45,46 as well as to experimental data [47][48][49][50][51][52][53][54][55][56][57][58] ; a good agreement is observed for all properties.…”

“…Comparison between the intermolecular N1-C2(top) and N1-H (middle) RDFs, calculated by DFT-MD simulation11 and those calculated using the fitted force field (FF). Bottom panel: comparison between the X-ray structure factor as obtained by experiment and calculated using the FF 39.…”