Potential Energy Surface for the Interaction of Helium with the Chiral Molecule Propylene Oxide

The discovery of propylene oxide in the interstellar medium has raised considerable interest about this molecule, which represents one of the simplest cases of chiral systems. In this paper, we present a quantum chemical study and a phenomenological approach, through the Pirani potential function, of the system He – propylene oxide in fourteen different configurations. Comparison of the optimized molecular structure at various level of theory, as well as a discussion on the two approaches is reported. The analytical form of the Pirani potential function permits future applications of classical simulations of molecular-beam collision experiments, especially to those related to chirality discrimination phenomena, in progress in our laboratory.

[1]  Vincenzo Aquilanti,et al.  Quantum chemical and dynamical approaches to intra and intermolecular kinetics: The CnH2nO (n = 1, 2, 3) molecules , 2011 .

[2]  Vincenzo Aquilanti,et al.  The hydrogen peroxide-rare gas systems: quantum chemical calculations and hyperspherical harmonic representation of the potential energy surface for atom-floppy molecule interactions. , 2007, The journal of physical chemistry. A.

[3]  Antonio Laganà,et al.  Water (H2O) m or Benzene (C6H6) n Aggregates to Solvate the K + ? , 2013, ICCSA.

[4]  Vincenzo Aquilanti,et al.  Interactions of Hydrogen Molecules with Halogen-Containing Diatomics from Ab Initio Calculations: Spherical-Harmonics Representation and Characterization of the Intermolecular Potentials. , 2016, The journal of physical chemistry. A.

[5]  U Valbusa,et al.  Stereodynamic effects in the adsorption of propylene molecules on Ag(001). , 2005, The journal of physical chemistry. B.

[6]  Dock-Chil Che,et al.  Aligned molecules: chirality discrimination in photodissociation and in molecular dynamics , 2013, Rendiconti Lincei.

[7]  Stefano Falcinelli,et al.  Double photoionization of propylene oxide: A coincidence study of the ejection of a pair of valence-shell electrons. , 2018, The Journal of chemical physics.

[8]  V. Aquilanti,et al.  Observed Molecular Alignment in Gaseous Streams and Possible Chiral Effects in Vortices and in Surface Scattering , 2007, Origins of Life and Evolution of Biospheres.

[9]  Alfredo Sánchez de Merás,et al.  Modelization of the $$\hbox {H}_{2}$$H2 adsorption on graphene and molecular dynamics simulation , 2017 .

[10]  Andrea Lombardi,et al.  Aqueous N-methylacetamide: New analytic potentials and a molecular dynamics study , 2016 .

[11]  Dock-Chil Che,et al.  Electrostatic hexapole state-selection of the asymmetric-top molecule propylene oxide. , 2010, The journal of physical chemistry. A.

[12]  Vincenzo Aquilanti,et al.  The Astrochemical Observatory: Molecules in the Laboratory and in the Cosmos , 2012 .

[13]  Fernando Pirani,et al.  Orienting and aligning molecules for stereochemistry and photodynamics. , 2005, Physical chemistry chemical physics : PCCP.

[14]  Assimo Maris,et al.  Free jet rotational spectrum of propylene oxide–krypton and modelling and ab initio calculations for propylene oxide–rare gas dimersElectronic supplementary information (ESI) available: Tables S1 and S2: Experimental transition frequencies of PRO⋯84Kr and PRO⋯86Kr complexes. See http://www.rsc.org/s , 2003 .

[15]  Andrea Lombardi,et al.  Chirality in molecular collision dynamics , 2018, Journal of physics. Condensed matter : an Institute of Physics journal.

[16]  Vincenzo Aquilanti,et al.  Molecular alignment and chirality in gaseous streams and vortices , 2013, Rendiconti Lincei.

[17]  Vincenzo Aquilanti,et al.  Quantum chemistry of C(3)H(6)O molecules: structure and stability, isomerization pathways, and chirality changing mechanisms. , 2010, The journal of physical chemistry. A.

[18]  Antonio Laganà,et al.  Carbon Oxides in Gas Flows and Earth and Planetary Atmospheres: State-to-State Simulations of Energy Transfer and Dissociation Reactions , 2013, ICCSA.

[19]  Dock-Chil Che,et al.  Hexapole-Oriented Asymmetric-Top Molecules and Their Stereodirectional Photodissociation Dynamics. , 2016, The journal of physical chemistry. A.

[20]  P. Decleva,et al.  Valence photoionization dynamics in circular dichroism of chiral free molecules: the methyl-oxirane. , 2005, The Journal of chemical physics.

[21]  Vincenzo Aquilanti,et al.  Chirality in molecular collisions , 2017 .

[22]  Fernando Pirani,et al.  A quantum mechanical view of molecular alignment and cooling in seeded supersonic expansions , 1999 .

[23]  H. J. Loesch,et al.  Brute Force Orientation of Asymmetric Top Molecules , 1997 .

[24]  Vincenzo Aquilanti,et al.  Aligned molecular collisions and a stereodynamical mechanism for selective chirality , 2011 .

[25]  M. Albertí,et al.  A force field for acetone: the transition from small clusters to liquid phase investigated by molecular dynamics simulations , 2016, Theoretical Chemistry Accounts.

[26]  Antonio Laganà,et al.  A Bond-Bond Portable Approach to Intermolecular Interactions: Simulations for N-methylacetamide and Carbon Dioxide Dimers , 2012, ICCSA.

[27]  Fernando Pirani,et al.  Collisional orientation of the benzene molecular plane in supersonic seeded expansions, probed by infrared polarized laser absorption spectroscopy and by molecular beam scattering , 2003 .

[28]  Yunjie Xu,et al.  Chiral self-recognition: direct spectroscopic detection of the homochiral and heterochiral dimers of propylene oxide in the gas phase. , 2006, Journal of the American Chemical Society.

[29]  Dock-Chil Che,et al.  Directions of chemical change: experimental characterization of the stereodynamics of photodissociation and reactive processes. , 2014, Physical chemistry chemical physics : PCCP.

[30]  Charles S. Parmenter,et al.  Aligning symmetric and asymmetric top molecules via single photon excitation , 1997 .

[31]  Vincenzo Aquilanti,et al.  Simulation of oriented collision dynamics of simple chiral molecules , 2011 .

[32]  Fernando Pirani,et al.  The collisional alignment of acetylene molecules in supersonic seeded expansions probed by infrared absorption and molecular beam scattering , 2007 .

[33]  Noelia Faginas Lago,et al.  Collisional Energy Exchange in CO _2 -N _2 Gaseous Mixtures , 2016, ICCSA.

[34]  Dock-Chil Che,et al.  Electrostatic hexapole state-selection of the asymmetric-top molecule propylene oxide: Rotational and orientational distributions☆ , 2012 .

[35]  Fernando Pirani,et al.  Velocity dependence of collisional alignment of oxygen molecules in gaseous expansions , 1994, Nature.

[36]  Fernando Pirani,et al.  Experimental benchmarks and phenomenology of interatomic forces: open-shell and electronic anisotropy effects , 2006 .

[37]  Fernando Pirani,et al.  The astrochemical observatory: Computational and theoretical focus on molecular chirality changing torsions around O - O and S - S bonds , 2017 .

[38]  Gaia Grossi,et al.  Range and strength of intermolecular forces for van der Waals complexes of the type H2Xn-Rg, with X = O, S and n = 1,2 , 2010 .

[39]  Vincenzo Aquilanti,et al.  A quantum chemical study of H2S2: Intramolecular torsional mode and intermolecular interactions with rare gases. , 2008, The Journal of chemical physics.

[40]  Geoffrey A. Blake,et al.  Discovery of the interstellar chiral molecule propylene oxide (CH3CHCH2O) , 2016, Science.

[41]  Dock-Chil Che,et al.  Control of conformers combining cooling by supersonic expansion of seeded molecular beams with hexapole selection and alignment: experiment and theory on 2-butanol. , 2014, Physical chemistry chemical physics : PCCP.

[42]  Andrea Lombardi,et al.  Modeling of energy transfer from vibrationally excited CO2 molecules: cross sections and probabilities for kinetic modeling of atmospheres, flows, and plasmas. , 2013, The journal of physical chemistry. A.

[43]  Vincenzo Aquilanti,et al.  Spherical and hyperspherical representation of potential energy surfaces for intermolecular interactions , 2011 .

[44]  P R P Barreto,et al.  Potential energy surface for the H2O-H2 system. , 2009, The journal of physical chemistry. A.

[45]  Vincenzo Aquilanti,et al.  Screens for Displaying Chirality Changing Mechanisms of a Series of Peroxides and Persulfides from Conformational Structures Computed by Quantum Chemistry , 2017, ICCSA.

[46]  Gaia Grossi,et al.  Accurate analytic intermolecular potential for the simulation of Na+ and K+ ion hydration in liquid water , 2015 .

[47]  Noelia Faginas Lago,et al.  Acetone Clusters Molecular Dynamics Using a Semiempirical Intermolecular Potential , 2016, ICCSA.

[48]  G. S. Maciel,et al.  Alignment and Chirality in Gaseous Flows , 2010 .

[49]  V. Aquilanti,et al.  Orientation of benzene in supersonic expansions, probed by IR-laser absorption and by molecular beam scattering. , 2001, Physical review letters.

[50]  V. Barone,et al.  Anharmonicity Effects in the Vibrational CD Spectra of Propylene Oxide , 2013 .

[51]  Antonio Laganà,et al.  An innovative synergistic grid approach to the computational study of protein aggregation mechanisms , 2014, Journal of Molecular Modeling.

[52]  Andrea Lombardi,et al.  A comparison of interatomic potentials for rare gas nanoaggregates , 2008 .

[53]  Vincenzo Aquilanti,et al.  The origin of chiral discrimination: supersonic molecular beam experiments and molecular dynamics simulations of collisional mechanisms , 2008 .

[54]  Martin Schütz,et al.  Molpro: a general‐purpose quantum chemistry program package , 2012 .

[55]  Noelia Faginas Lago,et al.  Acetone-Water Mixtures: Molecular Dynamics Using a Semiempirical Intermolecular Potential , 2017, ICCSA.

[56]  Fernando Pirani,et al.  The Astrochemical Observatory: Experimental and Computational Focus on the Chiral Molecule Propylene Oxide as a Case Study , 2017, ICCSA.

[57]  Michele Alagia,et al.  Circular dichroism in photoelectron spectroscopy of free chiral molecules: Experiment and theory on methyl-oxirane , 2004 .

[58]  Marzio Rosi,et al.  Modeling the Intermolecular Interactions and Characterization of the Dynamics of Collisional Autoionization Processes , 2013, ICCSA.

[59]  Dock-Chil Che,et al.  Stereodirectional images of molecules oriented by a variable-voltage hexapolar field: Fragmentation channels of 2-bromobutane electronically excited at two photolysis wavelengths. , 2017, The Journal of chemical physics.

[60]  M. Albertí,et al.  Ar solvation shells in K(+)-HFBz: from cluster rearrangement to solvation dynamics. , 2011, The journal of physical chemistry. A.

[61]  Noelia Faginas Lago,et al.  Competitive solvation of K+ by C6H6 and H2O in the K+-(C6H6)n-(H2O)m (n = 1–4; m = 1–6) aggregates , 2013 .