Theoretical Determination of Size Effects in Zeolite-Catalyzed Alcohol Dehydration
Abstract
In the upgrading of biomass pyrolysis vapors to hydrocarbons, dehydration accomplishes a primary objective of removing oxygen, and acidic zeolites represent promising catalysts for the dehydration reaction. Here, we utilized density functional theory calculations to estimate adsorption energetics and intrinsic kinetics of alcohol dehydration over H-ZSM-5, H-BEA, and H-AEL zeolites. The ONIOM (our Own N-layered Integrated molecular Orbital and molecular Mechanics) calculations of adsorption energies were observed to be inconsistent when benchmarked against QM (Quantum Mechanical)/Hartree–Fock and periodic boundary condition calculations. However, reaction coordinate calculations of adsorbed species and transition states were consistent across all levels considered. Comparison of ethanol, isopropanol (IPA), and tert-amyl alcohol (TAA) over these three zeolites allowed for a detailed examination of how confinement impacts on reaction mechanisms and kinetics. The TAA, seen to proceed via a carbocationic mechanism, was found to have the lowest activation barrier, followed by IPA and then ethanol, both of which dehydrate via a concerted mechanism. Barriers in H-BEA were consistently found to be lower than in H-ZSM-5 and H-AEL, attributed to late transition states and either elevated strain or inaccurately estimating long-range electrostatic interactions in H-AEL, respectively. Molecular dynamics simulations revealed that the diffusivity of these three alcohols in H-ZSM-5more »
- Authors:
-
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office
- OSTI Identifier:
- 1567023
- Report Number(s):
- NREL/JA-2700-74616
Journal ID: ISSN 2073-4344; CATACJ
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysts
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 9; Journal ID: ISSN 2073-4344
- Publisher:
- MDPI
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; biomass pyrolysis; alcohol dehydration; zeolite; DFT; ONIOM
Citation Formats
Kunz, Larissa Y., Bu, Lintao, Knott, Brandon C., Liu, Cong, Nimlos, Mark R., Assary, Rajeev S., Curtiss, Larry A., Robichaud, David J., and Kim, Seonah. Theoretical Determination of Size Effects in Zeolite-Catalyzed Alcohol Dehydration. United States: N. p., 2019.
Web. doi:10.3390/catal9090700.
Kunz, Larissa Y., Bu, Lintao, Knott, Brandon C., Liu, Cong, Nimlos, Mark R., Assary, Rajeev S., Curtiss, Larry A., Robichaud, David J., & Kim, Seonah. Theoretical Determination of Size Effects in Zeolite-Catalyzed Alcohol Dehydration. United States. https://doi.org/10.3390/catal9090700
Kunz, Larissa Y., Bu, Lintao, Knott, Brandon C., Liu, Cong, Nimlos, Mark R., Assary, Rajeev S., Curtiss, Larry A., Robichaud, David J., and Kim, Seonah. Wed .
"Theoretical Determination of Size Effects in Zeolite-Catalyzed Alcohol Dehydration". United States. https://doi.org/10.3390/catal9090700. https://www.osti.gov/servlets/purl/1567023.
@article{osti_1567023,
title = {Theoretical Determination of Size Effects in Zeolite-Catalyzed Alcohol Dehydration},
author = {Kunz, Larissa Y. and Bu, Lintao and Knott, Brandon C. and Liu, Cong and Nimlos, Mark R. and Assary, Rajeev S. and Curtiss, Larry A. and Robichaud, David J. and Kim, Seonah},
abstractNote = {In the upgrading of biomass pyrolysis vapors to hydrocarbons, dehydration accomplishes a primary objective of removing oxygen, and acidic zeolites represent promising catalysts for the dehydration reaction. Here, we utilized density functional theory calculations to estimate adsorption energetics and intrinsic kinetics of alcohol dehydration over H-ZSM-5, H-BEA, and H-AEL zeolites. The ONIOM (our Own N-layered Integrated molecular Orbital and molecular Mechanics) calculations of adsorption energies were observed to be inconsistent when benchmarked against QM (Quantum Mechanical)/Hartree–Fock and periodic boundary condition calculations. However, reaction coordinate calculations of adsorbed species and transition states were consistent across all levels considered. Comparison of ethanol, isopropanol (IPA), and tert-amyl alcohol (TAA) over these three zeolites allowed for a detailed examination of how confinement impacts on reaction mechanisms and kinetics. The TAA, seen to proceed via a carbocationic mechanism, was found to have the lowest activation barrier, followed by IPA and then ethanol, both of which dehydrate via a concerted mechanism. Barriers in H-BEA were consistently found to be lower than in H-ZSM-5 and H-AEL, attributed to late transition states and either elevated strain or inaccurately estimating long-range electrostatic interactions in H-AEL, respectively. Molecular dynamics simulations revealed that the diffusivity of these three alcohols in H-ZSM-5 were significantly overestimated by Knudsen diffusion, which will complicate experimental efforts to develop a kinetic model for catalytic fast pyrolysis.},
doi = {10.3390/catal9090700},
journal = {Catalysts},
number = 9,
volume = 9,
place = {United States},
year = {Wed Aug 21 00:00:00 EDT 2019},
month = {Wed Aug 21 00:00:00 EDT 2019}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Recent advances in heterogeneous catalysts for bio-oil upgrading via “ex situ catalytic fast pyrolysis”: catalyst development through the study of model compounds
journal, January 2014
- Ruddy, Daniel A.; Schaidle, Joshua A.; Ferrell III, Jack R.
- Green Chem., Vol. 16, Issue 2
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Recent Advances in Catalytic Conversion of Ethanol to Chemicals
journal, March 2014
- Sun, Junming; Wang, Yong
- ACS Catalysis, Vol. 4, Issue 4
A Correlation of Reaction Rates
journal, January 1955
- Hammond, George S.
- Journal of the American Chemical Society, Vol. 77, Issue 2
From laboratory experiments to simulation studies of methanol dehydration to produce dimethyl ether—Part I: Reaction kinetic study
journal, November 2013
- Tavan, Yadollah; Hosseini, Seyyed Hossein; Ghavipour, Mohammad
- Chemical Engineering and Processing: Process Intensification, Vol. 73
Intrinsic Kinetics of Ethanol Dehydration Over Lewis Acidic Ordered Mesoporous Silicate, Zr-KIT-6
journal, September 2014
- Pan, Qing; Ramanathan, Anand; Kirk Snavely, W.
- Topics in Catalysis, Vol. 57, Issue 17-20
Diffusion mechanism of hydrocarbons in zeolites—I. Theory
journal, April 1992
- Xiao, Jirong; Wei, James
- Chemical Engineering Science, Vol. 47, Issue 5
Ethanol Dehydration in HZSM-5 Studied by Density Functional Theory: Evidence for a Concerted Process
journal, April 2015
- Kim, Seonah; Robichaud, David J.; Beckham, Gregg T.
- The Journal of Physical Chemistry A, Vol. 119, Issue 15
Calorimetric Study of Alcohol and Nitrile Adsorption Complexes in H-ZSM-5
journal, May 1997
- Lee, C. -C.; Gorte, R. J.; Farneth, W. E.
- The Journal of Physical Chemistry B, Vol. 101, Issue 19
Performance of the M062X density functional against the ISOL set of benchmark isomerization energies for large organic molecules
journal, November 2010
- Rayne, Sierra; Forest, Kaya
- Nature Precedings
The Enthalpy-Entropy Relationship and its Implications for Organic Chemistry
journal, September 1955
- Leffler, John E.
- The Journal of Organic Chemistry, Vol. 20, Issue 9
13C solid state NMR evidence for the existence of isobutyl carbenium ion in the reaction of isobutyl alcohol dehydration in H-ZSM-5 zeolite
journal, January 1993
- Stepanov, Alexander G.; Zamaraev, Kirill I.
- Catalysis Letters, Vol. 19, Issue 2-3
Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995
- Plimpton, Steve
- Journal of Computational Physics, Vol. 117, Issue 1
Anharmonicity and Confinement in Zeolites: Structure, Spectroscopy, and Adsorption Free Energy of Ethanol in H-ZSM-5
journal, March 2016
- Alexopoulos, Konstantinos; Lee, Mal-Soon; Liu, Yue
- The Journal of Physical Chemistry C, Vol. 120, Issue 13
Conversion of ethanol over zeolite H-ZSM-5
journal, June 1994
- Schulz, Jürgen; Bandermann, Friedhelm
- Chemical Engineering & Technology, Vol. 17, Issue 3
Quantitatively Probing the Al Distribution in Zeolites
journal, May 2014
- Vjunov, Aleksei; Fulton, John L.; Huthwelker, Thomas
- Journal of the American Chemical Society, Vol. 136, Issue 23
Theoretical study of the adsorption of C1–C4 primary alcohols in H-ZSM-5
journal, January 2010
- Nguyen, Cuong M.; Reyniers, Marie-Françoise; Marin, Guy B.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 32
A comparative study of straw, perennial grasses and hardwoods in terms of fast pyrolysis products
journal, June 2013
- Greenhalf, C. E.; Nowakowski, D. J.; Harms, A. B.
- Fuel, Vol. 108
Dehydration reaction of bio-ethanol to ethylene over modified SAPO catalysts
journal, September 2010
- Chen, Yu; Wu, Yulong; Tao, Ling
- Journal of Industrial and Engineering Chemistry, Vol. 16, Issue 5
Comparison of four catalysts in the catalytic dehydration of ethanol to ethylene
journal, December 2008
- Zhang, Xian; Wang, Rijie; Yang, Xiaoxia
- Microporous and Mesoporous Materials, Vol. 116, Issue 1-3
Catalytic Upgrading of Biomass-Derived Compounds via C–C Coupling Reactions: Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5
journal, October 2015
- Liu, Cong; Evans, Tabitha J.; Cheng, Lei
- The Journal of Physical Chemistry C, Vol. 119, Issue 42
Rietveld profile analysis of calcined AlPO 4 -11 using pulsed neutron powder diffraction
journal, August 1988
- Richardson, J. W.; Pluth, J. J.; Smith, J. V.
- Acta Crystallographica Section B Structural Science, Vol. 44, Issue 4
Mechanistic Study of Alcohol Dehydration on γ-Al 2 O 3
journal, July 2012
- Roy, Sounak; Mpourmpakis, Giannis; Hong, Do-Young
- ACS Catalysis, Vol. 2, Issue 9
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007
- Zhao, Yan; Truhlar, Donald G.
- Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
Theoretical Investigation of Ethanol Conversion to Ethylene over H–ZSM–5 and Transition Metals–Exchanged ZSM–5
journal, November 2011
- Dumrongsakda, Parisa; Ruangpornvisuti, Vithaya
- Catalysis Letters, Vol. 142, Issue 1
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Carbocation Stability in H-ZSM5 at High Temperature
journal, November 2015
- Ferguson, Glen A.; Cheng, Lei; Bu, Lintao
- The Journal of Physical Chemistry A, Vol. 119, Issue 46
Dealuminated H−Y Zeolites: Influence of the Number and Type of Acid Sites on the Catalytic Activity for Isopropanol Dehydration
journal, September 2000
- Triantafillidis, Costas S.; Evmiridis, Nicholaos P.
- Industrial & Engineering Chemistry Research, Vol. 39, Issue 9
Increase in the number of acid sites of a H-ZSM5 zeolite during the dehydration of ethanol
journal, March 2007
- Takahara, Isao; Saito, Masahiro; Matsuhashi, Hiromi
- Catalysis Letters, Vol. 113, Issue 3-4
Ethanol transformation over HFAU, HBEA and HMFI zeolites presenting similar Brønsted acidity
journal, October 2009
- Madeira, F. Ferreira; Gnep, N. S.; Magnoux, P.
- Applied Catalysis A: General, Vol. 367, Issue 1-2
DFT study of ethanol dehydration catalysed by hematite
journal, January 2016
- Lopes, Juliana F.; Silva, Juliana C. M.; Cruz, Maurício T. M.
- RSC Advances, Vol. 6, Issue 46
The Hydrocarbon Pool in Ethanol-to-Gasoline over HZSM-5 Catalysts
journal, November 2008
- Johansson, Roger; Hruby, Sarah L.; Rass-Hansen, Jeppe
- Catalysis Letters, Vol. 127, Issue 1-2
Mechanistic Studies on the Transformation of Ethanol into Ethene over Fe-ZSM-5 Zeolite
journal, November 2012
- Maihom, Thana; Khongpracha, Pipat; Sirijaraensre, Jakkapan
- ChemPhysChem, Vol. 14, Issue 1
Improved Force-Field Parameters for QM/MM Simulations of the Energies of Adsorption for Molecules in Zeolites and a Free Rotor Correction to the Rigid Rotor Harmonic Oscillator Model for Adsorption Enthalpies
journal, January 2015
- Li, Yi-Pei; Gomes, Joseph; Mallikarjun Sharada, Shaama
- The Journal of Physical Chemistry C, Vol. 119, Issue 4
Diffusion of aromatic hydrocarbons in hierarchical mesoporous H-ZSM-5 zeolite
journal, August 2018
- Bu, Lintao; Nimlos, Mark R.; Robichaud, David J.
- Catalysis Today, Vol. 312
Consideration of the Aluminum Distribution in Zeolites in Theoretical and Experimental Catalysis Research
journal, December 2017
- Knott, Brandon C.; Nimlos, Claire T.; Robichaud, David J.
- ACS Catalysis, Vol. 8, Issue 2
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Mechanism of the reductive dehydration of ethanol into C3+ alkanes over the commercial alumina—platinum catalyst AP-64
journal, January 2016
- Zavelev, D. E.; Chistyakov, A. V.; Zhidomirov, G. M.
- Kinetics and Catalysis, Vol. 57, Issue 1
Compensation effect in isopropanol dehydration over heteropoly acid catalysts at a gas–solid interface
journal, September 2012
- Bond, Geoffrey C.; Frodsham, Sarah J.; Jubb, Paul
- Journal of Catalysis, Vol. 293
Surface acidity modifications induced by thermal treatments and acid leaching on microcrystalline H-BEA zeolite. A FTIR, XRD and MAS-NMR study
journal, January 2000
- Trombetta, Marcella; Busca, Guido; Storaro, Loretta
- Physical Chemistry Chemical Physics, Vol. 2, Issue 15
Effects of the Zeolite Framework on the Adsorptions and Hydrogen-Exchange Reactions of Unsaturated Aliphatic, Aromatic, and Heterocyclic Compounds in ZSM-5 Zeolite: A Combination of Perturbation Theory (MP2) and a Newly Developed Density Functional Theory (M06-2X) in ONIOM Scheme
journal, November 2009
- Boekfa, Bundet; Choomwattana, Saowapak; Khongpracha, Pipat
- Langmuir, Vol. 25, Issue 22
13C CP/MAS NMR study of isobutyl alcohol dehydration on H-ZSM-5 zeolite. Evidence for the formation of stable isobutyl silyl ether intermediate
journal, January 1992
- Stepanov, Alexander G.; Romannikov, Vyacheslav N.; Zamaraev, Kirill I.
- Catalysis Letters, Vol. 13, Issue 4
13C CP/MAS and2H NMR study of tert-butyl alcohol dehydration on H-ZSM-5 zeolite. Evidence for the formation of tert-butyl cation and tert-butyl silyl ether intermediates
journal, January 1992
- Stepanov, Alexander G.; Zamaraev, Kirill I.; Thomas, John M.
- Catalysis Letters, Vol. 13, Issue 4
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Ethylene from ethanol over zeolite catalysts
journal, January 1987
- Le Van Mao, R.; Levesque, P.; McLaughlin, G.
- Applied Catalysis, Vol. 34
Dehydration of Ethanol into Ethylene over Solid Acid Catalysts
journal, December 2005
- Takahara, Isao; Saito, Masahiro; Inaba, Megumu
- Catalysis Letters, Vol. 105, Issue 3-4
Exploring Low-Temperature Dehydrogenation at Ionic Cu Sites in Beta Zeolite To Enable Alkane Recycle in Dimethyl Ether Homologation
journal, April 2017
- Farberow, Carrie A.; Cheah, Singfoong; Kim, Seonah
- ACS Catalysis, Vol. 7, Issue 5
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Ethylene Formation by Catalytic Dehydration of Ethanol with Industrial Considerations
journal, December 2012
- Fan, Denise; Dai, Der-Jong; Wu, Ho-Shing
- Materials, Vol. 6, Issue 1
Brønsted Acidity of Isomorphously Substituted ZSM-5 by B, Al, Ga, and Fe. Density Functional Investigations
journal, September 2002
- Yuan, S. P.; Wang, J. G.; Li, Y. W.
- The Journal of Physical Chemistry A, Vol. 106, Issue 35
Diffusion of Biomass Pyrolysis Products in H-ZSM-5 by Molecular Dynamics Simulations
journal, December 2016
- Bu, Lintao; Nimlos, Mark R.; Robichaud, David J.
- The Journal of Physical Chemistry C, Vol. 121, Issue 1
Efficient Approach for the Computational Study of Alcohol and Nitrile Adsorption in H-ZSM-5
journal, February 2012
- Van der Mynsbrugge, Jeroen; Hemelsoet, Karen; Vandichel, Matthias
- The Journal of Physical Chemistry C, Vol. 116, Issue 9
Structural and electronic features of a Broensted acid site in H-ZSM-5
journal, June 1993
- Cook, Stephen J.; Chakraborty, Arup K.; Bell, Alex T.
- The Journal of Physical Chemistry, Vol. 97, Issue 25
Dehydration of Ethanol to Ethylene
journal, July 2013
- Zhang, Minhua; Yu, Yingzhe
- Industrial & Engineering Chemistry Research, Vol. 52, Issue 28
Investigation into the shape selectivity of zeolite catalysts for biomass conversion
journal, April 2011
- Jae, Jungho; Tompsett, Geoffrey A.; Foster, Andrew J.
- Journal of Catalysis, Vol. 279, Issue 2, p. 257-268
Heteropolyacid supported on montmorillonite catalyst for dehydration of dilute bio-ethanol
journal, August 2011
- Bokade, Vijay V.; Yadav, Ganapati D.
- Applied Clay Science, Vol. 53, Issue 2
Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements
journal, September 2007
- Stewart, James J. P.
- Journal of Molecular Modeling, Vol. 13, Issue 12
Production of Ethylene from Hydrous Ethanol on H-ZSM-5 under Mild Conditions
journal, November 1997
- Phillips, Cory B.; Datta, Ravindra
- Industrial & Engineering Chemistry Research, Vol. 36, Issue 11
Dehydration of isopropyl alcohol used as an indicator of the type and strength of catalyst acid centres
journal, October 2005
- Turek, W.; Haber, J.; Krowiak, A.
- Applied Surface Science, Vol. 252, Issue 3
Ethanol conversion over ion-exchanged ZSM-5 zeolites
journal, March 1990
- Bun, Sawane; Nishiyama, Satoru; Tsuruya, Shigeru
- Applied Catalysis, Vol. 59, Issue 1
Catalytic activity of Brønsted acid sites in zeolites: Intrinsic activity, rate-limiting step, and influence of the local structure of the acid sites
journal, December 2006
- Xu, B.; Sievers, C.; Hong, S.
- Journal of Catalysis, Vol. 244, Issue 2
Conversion of ethanol on HZSM-5 modified zeolite, according to data from in situ spectrokinetic studies
journal, May 2013
- Tret’yakov, V. F.; Nhu, Chan Thi Quynh; Tret’yakov, K. V.
- Russian Journal of Physical Chemistry A, Vol. 87, Issue 6
Implications of Transition State Confinement within Small Voids for Acid Catalysis
journal, July 2014
- Jones, Andrew J.; Zones, Stacey I.; Iglesia, Enrique
- The Journal of Physical Chemistry C, Vol. 118, Issue 31
Dehydration of ethanol over zeolites, silica alumina and alumina: Lewis acidity, Brønsted acidity and confinement effects
journal, March 2015
- Phung, Thanh Khoa; Proietti Hernández, Loriana; Lagazzo, Alberto
- Applied Catalysis A: General, Vol. 493
Furan Production from Glycoaldehyde over HZSM-5
journal, April 2016
- Kim, Seonah; Evans, Tabitha J.; Mukarakate, Calvin
- ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 5
DFT-based microkinetic modeling of ethanol dehydration in H-ZSM-5
journal, July 2016
- Alexopoulos, Konstantinos; John, Mathew; Van der Borght, Kristof
- Journal of Catalysis, Vol. 339
Effect of Fe-loading and reaction temperature on the production of olefins from ethanol by Fe/H-ZSM-5 zeolite catalysts
journal, June 2009
- Inaba, Megumu; Murata, Kazuhisa; Takahara, Isao
- Reaction Kinetics and Catalysis Letters, Vol. 97, Issue 1
The effects of local structural relaxation on aluminum siting within H-ZSM-5
journal, January 1991
- Lonsinger, Stephen R.; Chakraborty, Arup K.; Theodorou, Doros N.
- Catalysis Letters, Vol. 11, Issue 2
Transformation of ethanol into hydrocarbons on ZSM-5 zeolites modified with iron in different ways
journal, July 2008
- Calsavara, Valmir; Baesso, Mauro Luciano; Fernandes-Machado, Nádia Regina Camargo
- Fuel, Vol. 87, Issue 8-9
Transformation of Oxygenate Components of Biomass Pyrolysis Oil on a HZSM-5 Zeolite. I. Alcohols and Phenols
journal, May 2004
- Gayubo, Ana G.; Aguayo, Andrés T.; Atutxa, Alaitz
- Industrial & Engineering Chemistry Research, Vol. 43, Issue 11
Theoretical Study of the Adsorption of the Butanol Isomers in H-ZSM-5
journal, April 2011
- Nguyen, Cuong M.; Reyniers, Marie-Françoise; Marin, Guy B.
- The Journal of Physical Chemistry C, Vol. 115, Issue 17
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
Transformation of ethanol into hydrocarbons on ZSM-5 zeolites modified with iron in different ways
journal, July 2008
- Calsavara, Valmir; Baesso, Mauro Luciano; Fernandes-Machado, Nádia Regina Camargo
- Fuel, Vol. 87, Issue 8-9
Energy production from biomass (part 1): overview of biomass
journal, May 2002
- McKendry, Peter
- Bioresource Technology, Vol. 83, Issue 1
Performance of the M062X density functional against the ISOL set of benchmark isomerization energies for large organic molecules
journal, November 2010
- Rayne, Sierra; Forest, Kaya
- Nature Precedings
Assessing the quality of the random phase approximation for lattice constants and atomization energies of solids
journal, March 2010
- Harl, Judith; Schimka, Laurids; Kresse, Georg
- Physical Review B, Vol. 81, Issue 11