TY - JOUR
T1 - Second-order many-body perturbation study on thermal expansion of solid carbon dioxide
AU - Li, Jinjin
AU - Sode, Olaseni
AU - Hirata, So
N1 - Publisher Copyright:
© 2014 American Chemical Society.
Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.
PY - 2015/1/13
Y1 - 2015/1/13
N2 - An embedded-fragment ab initio second-order many-body perturbation (MP2) method is applied to an infinite three-dimensional crystal of carbon dioxide phase I (CO2-I), using the aug-cc-pVDZ and aug-cc-pVTZ basis sets, the latter in conjunction with a counterpoise correction for the basis-set superposition error. The equation of state, phonon frequencies, bulk modulus, heat capacity, Grüneisen parameter (including mode Grüneisen parameters for acoustic modes), thermal expansion coefficient (α), and thermal pressure coefficient (β) are computed. Of the factors that enter the expression of α, MP2 reproduces the experimental values of the heat capacity, Grüneisen parameter, and molar volume accurately. However, it proves to be exceedingly difficult to determine the remaining factor, the bulk modulus (B0), the computed value of which deviates from the observed value by 50-100%. As a result, α calculated by MP2 is systematically too low, while having the correct temperature dependence. The thermal pressure coefficient, β = αB0, which is independent of B0, is more accurately reproduced by theory up to 100 K.
AB - An embedded-fragment ab initio second-order many-body perturbation (MP2) method is applied to an infinite three-dimensional crystal of carbon dioxide phase I (CO2-I), using the aug-cc-pVDZ and aug-cc-pVTZ basis sets, the latter in conjunction with a counterpoise correction for the basis-set superposition error. The equation of state, phonon frequencies, bulk modulus, heat capacity, Grüneisen parameter (including mode Grüneisen parameters for acoustic modes), thermal expansion coefficient (α), and thermal pressure coefficient (β) are computed. Of the factors that enter the expression of α, MP2 reproduces the experimental values of the heat capacity, Grüneisen parameter, and molar volume accurately. However, it proves to be exceedingly difficult to determine the remaining factor, the bulk modulus (B0), the computed value of which deviates from the observed value by 50-100%. As a result, α calculated by MP2 is systematically too low, while having the correct temperature dependence. The thermal pressure coefficient, β = αB0, which is independent of B0, is more accurately reproduced by theory up to 100 K.
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U2 - 10.1021/ct500983k
DO - 10.1021/ct500983k
M3 - Article
C2 - 26574220
AN - SCOPUS:84921418219
SN - 1549-9618
VL - 11
SP - 224
EP - 229
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 1
ER -