We provide a first-principles methodology to obtain converged results
for the lattice energy of crystals of small, neutral organic molecules.
In particular, we determine the lattice energy of crystalline benzene
using an additive system based on the individual interaction energies
of benzene dimers. Enthalpy corrections are estimated so that the
lattice energy can be directly compared to the experimentally determined
sublimation energy. Our best estimate of the sublimation energy is
49.4 kJ mol-1, just over the typical experimentally reported values
of 43-47 kJ mol-1. Our results underscore the necessity of using
highly correlated electronic structure methods to determine thermodynamic
properties within chemical accuracy. The first coordination sphere
contributes about 90 % of the total lattice energy, and the second
coordination sphere contributes the remaining 10 %. Three-body interactions
are determined to be negligible.
%0 Journal Article
%1 Ringer2008
%A Ringer, A
%A Sherrill, C. David
%D 2008
%J Chemistry : a European journal
%K ; ;benzene ab calculations chemistry computer dimerization energy, initio lattice science surface
%N 8
%P 2542-2547
%R 10.1002/chem.200701622
%T First principles computation of lattice energies of organic solids:
The benzene crystal
%U http://tinyurl.sfx.mpg.de/nsbh
%V 14
%X We provide a first-principles methodology to obtain converged results
for the lattice energy of crystals of small, neutral organic molecules.
In particular, we determine the lattice energy of crystalline benzene
using an additive system based on the individual interaction energies
of benzene dimers. Enthalpy corrections are estimated so that the
lattice energy can be directly compared to the experimentally determined
sublimation energy. Our best estimate of the sublimation energy is
49.4 kJ mol-1, just over the typical experimentally reported values
of 43-47 kJ mol-1. Our results underscore the necessity of using
highly correlated electronic structure methods to determine thermodynamic
properties within chemical accuracy. The first coordination sphere
contributes about 90 % of the total lattice energy, and the second
coordination sphere contributes the remaining 10 %. Three-body interactions
are determined to be negligible.
@article{Ringer2008,
abstract = {We provide a first-principles methodology to obtain converged results
for the lattice energy of crystals of small, neutral organic molecules.
In particular, we determine the lattice energy of crystalline benzene
using an additive system based on the individual interaction energies
of benzene dimers. Enthalpy corrections are estimated so that the
lattice energy can be directly compared to the experimentally determined
sublimation energy. Our best estimate of the sublimation energy is
49.4 kJ mol-1, just over the typical experimentally reported values
of 43-47 kJ mol-1. Our results underscore the necessity of using
highly correlated electronic structure methods to determine thermodynamic
properties within chemical accuracy. The first coordination sphere
contributes about 90 % of the total lattice energy, and the second
coordination sphere contributes the remaining 10 %. Three-body interactions
are determined to be negligible.},
added-at = {2009-10-30T10:04:05.000+0100},
author = {Ringer, A and Sherrill, C. David},
biburl = {https://www.bibsonomy.org/bibtex/2d118007e293af74645a62981d33ee064/jfischer},
doi = {10.1002/chem.200701622},
interhash = {9511fb8014c2d2d612cd10901d1e5eef},
intrahash = {d118007e293af74645a62981d33ee064},
issn = {0947-6539},
journal = {Chemistry : a European journal},
keywords = {; ;benzene ab calculations chemistry computer dimerization energy, initio lattice science surface},
number = 8,
pages = {2542-2547},
timestamp = {2009-10-30T10:04:18.000+0100},
title = {First principles computation of lattice energies of organic solids:
The benzene crystal},
url = {http://tinyurl.sfx.mpg.de/nsbh},
volume = 14,
year = 2008
}