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Title: Iodine recombination in xenon solvent: Clusters in the gas to liquid-like state transition

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/5.0260087 · OSTI ID:3364826
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Pennsylvania State Univ., University Park, PA (United States)
  2. Stanford Univ., CA (United States)
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Supercritical fluids (SCFs) have attracted significant attention as solvents for chemical reactions due to their unique properties, such as high diffusivity, low viscosity, and tunable solvation properties. These properties profoundly influence reaction kinetics and are often attributed to the formation of molecular clusters within SCFs. To study the effect of supercritical solvent on chemical reactivity and dynamics of reactions, one needs to understand the dynamics of clusters in supercritical fluid. Extensive experiments on the photodissociation and recombination of iodine in supercritical fluids served as a model system for understanding these effects. Experimental studies have been complemented by theoretical and computational investigations, which mostly employ Monte Carlo or empirical molecular dynamics simulations. However, computational studies using non-reactive force fields and ab initio approaches present challenges in capturing reactive processes at larger scales within supercritical fluids. Here, in this work, we developed the ReaxFF parameters by training against quantum mechanics data. ReaxFF reactive force field based molecular dynamics simulations were performed, studying the dynamics of a xenon solvent and cage effect at different thermodynamic conditions for the iodine recombination reaction. We show that the conditions near the critical point are the optimal conditions to study the cage effect. We show that the average lifetime of xenon clusters ranging between 5 and 11 ps is comparable to iodine geminate recombination. Our simulation results of iodine recombination in xenon solvent demonstrate the higher probability of iodine molecule formation in the presence of xenon clusters. Finally, we show that the supercritical condition exhibits the highest recombination rate for iodine atoms.

Research Organization:
Stanford Univ., CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0022222; SC0026165
OSTI ID:
3364826
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 19 Vol. 162; ISSN 1089-7690; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (51)

The Complete Active Space Self-Consistent Field Method and its Applications in Electronic Structure Calculations book January 1987
Chemistry with ADF journal January 2001
Semiempirical GGA-type density functional constructed with a long-range dispersion correction journal January 2006
CHARMM general force field: A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields journal January 2009
Recombination of iodine atoms in gases at high pressures journal September 1972
Photolytic cage effect of iodine in gases at high pressures journal January 1974
Picosecond studies of the cage effect and collision induced predissociation of iodine in liquids journal March 1974
Predissociation and geminate recombination kinetics of I2 in liquid xenon and CCl4 journal January 1982
Atom recombination in dense gases and fluids—a stochastic model journal February 1985
On the history of key empirical intermolecular potentials journal October 2023
Molecular dynamic simulation of aluminum–water reactions using the ReaxFF reactive force field journal May 2011
Atomistic-scale simulations of chemical reactions: Bridging from quantum chemistry to engineering
  • Russo, Michael F.; van Duin, Adri C. T.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 269, Issue 14 https://doi.org/10.1016/j.nimb.2010.12.053
journal July 2011
Evaluating the Ability of Selected Force Fields to Simulate Hydrocarbons as a Function of Temperature and Pressure Using Molecular Dynamics journal February 2021
Quantum Chemical Study of Supercritical Carbon Dioxide Effects on Combustion Kinetics journal May 2017
Influence of Cage Effects in Directing the Outcome of C–X Bond Forming Reactions journal October 2023
A local density functional study of the structure and vibrational frequencies of molecular transition-metal compounds journal August 1992
Xenon as a supercritical solvent journal June 1984
Liquid xenon: an effective inert solvent for carbon-hydrogen oxidative addition reactions journal August 1989
Structure and thermal reactions of dihydrogen complexes: the IR characterization of M(CO)5(H2) (M = chromium, molybdenum, and tungsten) and cis-Cr(CO)4(H2)2 in liquid xenon solution and the formation of HD during exchange of hydrogen and deuterium journal June 1986
Photolytic cage effect. Monte-Carlo experiments journal March 1972
The Effect of Viscosity on the Quantum Yield for Iodine Dissociation journal April 1960
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids journal January 1996
The NIST Chemistry WebBook:  A Chemical Data Resource on the Internet † journal September 2001
Theoretical Study of Water Cluster Catalyzed Decomposition of Formic Acid journal April 2014
ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation journal February 2008
Development and Application of a ReaxFF Reactive Force Field for Oxidative Dehydrogenation on Vanadium Oxide Catalysts journal August 2008
Cage Effect in Supercritical Fluids and Compressed Gases in the Photolysis of an Asymmetrically Substituted Diazene journal April 2009
All-Atom Empirical Potential for Molecular Modeling and Dynamics Studies of Proteins † journal April 1998
Femtosecond dynamics of dissociation and recombination in solvent cages journal July 1993
The Widom line as the crossover between liquid-like and gas-like behaviour in supercritical fluids journal June 2010
The ReaxFF reactive force-field: development, applications and future directions journal March 2016
Supercritical fluids behave as complex networks journal April 2023
Delft molecular mechanics: a new approach to hydrocarbon force fields. Inclusion of a geometry-dependent charge calculation journal January 1994
Accurate Coulomb-fitting basis sets for H to Rn journal January 2006
Some remarks about free radicals and the photochemistry of solutions journal January 1934
Spectroscopic properties and potential energy curves of low-lying electronic states of RuC journal April 2004
Molecular Clusters in Imperfect Gases journal April 1955
The Approximate Rate of Exchange between Iodine Atoms and Molecules journal May 1950
Stochastic trajectory simulation of iodine recombination in liquids journal January 1980
The photolytic cage effect of iodine in gases and liquids journal February 1983
Photolytic cage effect and atom recombination of iodine in compressed gases and liquids: Experiments and simple models journal July 1984
A large-scale and long-time molecular dynamics study of supercritical Lennard-Jones fluid. An analysis of high temperature clusters journal August 1997
Injection of Fluids into Supercritical Environments journal January 2006
Molecular dynamics and chemical reactivity journal January 1977
Supercritical Xe as Propellant in Satellite Electric Propulsion System: Experimental Study on Thermal Physical Properties journal June 2019
Generalized Gradient Approximation Made Simple journal October 1996
Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation journal February 1992
Applications of Supercritical Fluids journal June 2010
The Nature of Simple Photodissociation Reactions in Liquids on Ultrafast Time Scales journal October 1988
A density functional theory analysis of the adsorption and surface chemistry of inorganic iodine species on graphitea journal May 2023
Cage Effect under Photolysis in Polymer Matrices journal February 2019

Figures / Tables (18)

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Related Subjects

Cage effect
Chemical elements
Chemical kinetics and dynamics
Geminate recombination
Molecular dynamics
Molecule formation
Phase transitions
Photodissociation
Reactive force field
Recombination reactions