Prediction of a high-pressure phase transition and other properties of solid<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">CO</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>at low temperatures

Kuchta, B; Etters, R. D.

doi:10.1103/physrevb.38.6265

Cited by 50 publications

(64 citation statements)

References 18 publications

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“…We use MP2 with the exact electronic Hamiltonian (as opposed to empirical or modified Hamiltonians in previous calculations), which is the simplest theory that can describe all cohesive interactions in solid CO 2 simultaneously, accurately and on an equal footing. MP2/aug-cc-pVDZ predicts the transition pressure of 13 GPa (or a few GPa less at a larger basis set) at 0 K with small temperature dependence, which is in line with many experimental reports, while exposing the limitations of the DFT calculation 34 , predicting a higher transition pressure and greater temperature dependence, and of the empirical calculations [31][32][33] , yielding too low a transition pressure.…”

supporting

confidence: 54%

“…3. In Table 1, the calculated lattice constants and tilt angle (j) at 11.8 GPa are compared with the experimental values 20 and with those obtained with the empirical force field by Kuchta and Etters 31 . Note that in addition to a, b, c, and j, the CO bond lengths in both CO 2 -I and III have also been optimized at each pressure in our calculations, which, therefore, constitute full optimization with only symmetry constraints imposed.…”

Section: Resultsmentioning

confidence: 99%

“…In fact, the high-pressure phase transition from I to III was computationally predicted by Kuchta and Etters [31][32][33] prior to the x-ray diffraction study 20 . Their calculated value of the CO 2 tilt angle j of 52°was in exact agreement with the observed.…”

mentioning

confidence: 99%

“…Those of Kuchta and Etters [31][32][33] were based on empirical force fields and their predicted transition pressure of 4.3 GPa was too low. The DFT calculations 34 also lacked dispersion interactions, which were shown by us 35 to be crucial cohesive forces in CO 2 -I.…”

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A solid–solid phase transition in carbon dioxide at high pressures and intermediate temperatures

Sode

Voth

et al. 2013

Nat Commun

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Despite its terrestrial abundance and astrochemical significance, many aspects of the phase diagram of solid carbon dioxide remain uncertain or unknown. The observed transition pressures from cubic to orthorhombic phase range widely from 2.5 GPa at 80 K to above 18 GPa at room temperature. The vibrational Raman bands that appear at higher pressure and serve as a decisive proof of the existence of the orthorhombic phase have never been assigned. Here we introduce a general ab initio computational method that can predict the Gibbs free energies and thus phase diagrams of molecular crystals. Using this with secondorder Møller-Plesset perturbation theory, we obtain the transition pressure of 13 GPa at 0 K with small temperature dependence, which is in line with many experiments. We also computationally reproduce the vibrational Raman bands and explain the pressure dependence of the structure parameters and Raman band positions of both phases quantitatively.

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confidence: 54%

Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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