First principles models of the interactions of methane and carbon dioxide

Oakley, Mark T.; Do, Hainam; Wheatley, Richard J.

doi:10.1016/j.fluid.2009.11.011

Cited by 18 publications

(11 citation statements)

References 20 publications

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“…Two ab initio potentials are available in the literature for the CH 4 -CO 2 molecule pair [18,19]. Oakley et al [18] calculated the interaction energies only at the MP2 level of theory, which is not accurate enough for the present purpose. Pai and Bae [19] used the much more accurate CCSD(T) method [20].…”

Section: Introductionmentioning

confidence: 99%

Cross second virial coefficients and dilute gas transport properties of the (CH 4 + CO 2 ), (CH 4 + H 2 S), and (H 2 S + CO 2 ) systems from accurate intermolecular potential energy surfaces

Hellmann

Bich

Vesovic

2016

The Journal of Chemical Thermodynamics

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The cross second virial coefficient and the dilute gas shear viscosity, thermal conductivity, and binary diffusion coefficient have been calculated for (CH 4 + CO 2 ), (CH 4 + H 2 S), and (H 2 S + CO 2 ) mixtures in the temperature range from (150 to 1200) K. The cross second virial coefficient was obtained using the Mayer-sampling Monte Carlo approach, while the transport properties were evaluated by means of the classical trajectory method. State-of-the-art intermolecular potential energy surfaces for the like and unlike species interactions were employed in the calculations. All potential energy surfaces are based on highly accurate quantum-chemical ab initio calculations, with the potentials for the unlike interactions reported in this work and those for the like interactions taken from our previous studies of the pure gases. The computed transport property values are in good agreement with the few available experimental data, which are limited to (CH 4 + CO 2 ) mixtures close to room temperature. The lack of reliable data makes the values of the thermophysical properties calculated in this work currently the most accurate estimates for lowdensity (CH 4 + CO 2 ), (CH 4 + H 2 S), and (H 2 S + CO 2 ) mixtures. Tables of recommended values for all investigated thermophysical properties as a function of temperature and composition are provided.

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Section: Introductionmentioning

confidence: 99%

Cross second virial coefficients and dilute gas transport properties of the (CH 4 + CO 2 ), (CH 4 + H 2 S), and (H 2 S + CO 2 ) systems from accurate intermolecular potential energy surfaces

Hellmann

Bich

Vesovic

2016

The Journal of Chemical Thermodynamics

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“…We compare the second virial coefficients of CO 2 calculated with our best pair potential (CBS-ad), 8 with those calculated with the empirical Trappe-EH potential 19 ( Table V). The empirical potential reproduces the phase coexistence curve of CO 2 , but underestimates the virial coefficients, because it implicitly includes multibody interactions as well as pair interactions.…”

Section: Resultsmentioning

confidence: 99%

“…In our work on CH 4 , 8 we found that a Lennard-Jones 6-12 potential makes the repulsive wall too steep for interactions involving hydrogen atoms. Therefore, n = 8 is used for any pairs including a hydrogen atom and n = 12 is used for all other interactions.…”

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confidence: 86%

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First principles predictions of thermophysical properties of refrigerant mixtures

Oakley

Hirst

et al. 2011

The Journal of Chemical Physics

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Prediction of the phase behavior of acetonitrile and methanol with ab initio pair potentials. II. The mixture J. Chem. Phys. 116, 7637 (2002) We present pair potentials for fluorinated methanes and their dimers with CO 2 based on ab initio potential energy surfaces. These potentials reproduce the experimental second virial coefficients of the pure fluorinated methanes and their mixtures with CO 2 without adjustment. Ab initio calculations on trimers are used to model the effects of nonadditive dispersion and induction. Simulations using these potentials reproduce the experimental phase-coexistence properties of CH 3 F within 10% over a wide range of temperatures. The phase coexistence curve of the mixture of CH 2 F 2 and CO 2 is reproduced with an error in the mole fractions of both phases of less than 0.1. The potentials described here are based entirely on ab initio calculations, with no empirical fits to improve the agreement with experiment.

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“…The case of n = 2 turns out to be so robust that all theoretical predictions are qualitatively the same, as shown in Figure and Table . Relative to the most stable fragments CO 2 and CH 4 (Σ), the van der Waals complex (G) is more stable by 2–5 kJ/mol, depending on the level and on the somewhat problematic inclusion of harmonic zero‐point energy corrections. Contiguous molecules are much higher in energy, starting with acetic acid (G M ), followed by methyl formate and finally glycolaldehyde as the sugar model system .…”

Section: Stepwise Increase Of N For Cnh2nonmentioning

confidence: 99%

The Guinness Molecules for the Carbohydrate Formula

Altnöder

Krüger

Borodin

et al. 2014

The Chemical Record

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A systematic review and analysis of the most stable spatial arrangements of n carbon, n oxygen, and 2n hydrogen atoms including vibrational zero-point energy up to n = 5 shows that small-molecule aggregates win, typically followed by thermally unstable molecules, before kinetically stable molecules and finally carbohydrates are found. Near n ≈ 60 a crossover to carbon allotropes and ice as the global minimum structure is expected and the asymptotic limit is most likely graphite and ice. Implications for astrochemical and fermentation processes are discussed. Density functionals like B3LYPD3 are found to describe these energy sequences quite poorly, mostly due to an overestimated stability of carbon in high oxidation states.

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First principles models of the interactions of methane and carbon dioxide

Cited by 18 publications

References 20 publications

Cross second virial coefficients and dilute gas transport properties of the (CH 4 + CO 2 ), (CH 4 + H 2 S), and (H 2 S + CO 2 ) systems from accurate intermolecular potential energy surfaces

Cross second virial coefficients and dilute gas transport properties of the (CH 4 + CO 2 ), (CH 4 + H 2 S), and (H 2 S + CO 2 ) systems from accurate intermolecular potential energy surfaces

First principles predictions of thermophysical properties of refrigerant mixtures

The Guinness Molecules for the Carbohydrate Formula

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