Estimating Systematic Error and Uncertainty in Ab Initio Thermochemistry: I. Atomization Energies of Hydrocarbons in the ATOMIC(hc) Protocol

Journal of Chemical Theory and Computation
Dirk Bakowies

Abstract

Research in ab initio quantum chemistry has produced an increasing number of thermochemistry protocols, serving different needs from benchmark-level accuracy for small molecules to "chemical accuracy" for larger molecules. While in experimental thermochemistry it is accepted standard to report results complete with intervals of 95% confidence, so far only few of the most advanced theoretical approaches have followed suit, based either on statistical comparison to well-established experimental data or careful assessment of high level theoretical results for individual molecules. Here we report on the development of intrinsic uncertainty estimates for the ATOMIC protocol in applications to hydrocarbons. ATOMIC is a theoretical procedure geared toward larger molecules and based on the ab initio implementation of bond separation reactions (BSRs) to reduce errors of mid-level composite approaches. Each of the components contributing to the bottom-of-the-well atomization energy (E_{A,e}) is scrutinized for possible error by comparison to a large number of very high-level results, including complete-basis-set estimates of CCSDT(Q) bond separation energies for 83 hydrocarbons up to the size of naphthalene. Some of the observations are:...Continue Reading

References

Jul 23, 2004·The Journal of Chemical Physics·A Daniel BoeseJurgen Gauss
Jan 7, 2005·The Journal of Chemical Physics·Attila TajtiJohn F Stanton
Aug 20, 2005·The Journal of Chemical Physics·Yannick J BombleJürgen Gauss
Dec 17, 2005·The Journal of Chemical Physics·Mihály Kállay, Jürgen Gauss
Mar 25, 2006·The Journal of Chemical Physics·Nathan J DeYonkerAngela K Wilson
Sep 27, 2006·The Journal of Chemical Physics·Nathan J DeYonkerAngela K Wilson
Oct 18, 2006·The Journal of Chemical Physics·Amir KartonBranko Ruscic
Mar 9, 2007·The Journal of Chemical Physics·Larry A CurtissKrishnan Raghavachari
Apr 13, 2007·Journal of Chemical Information and Modeling·Karen L SchuchardtTheresa L Windus
Jul 14, 2007·The Journal of Chemical Physics·Attila TajtiJürgen Gauss
Aug 21, 2007·The Journal of Chemical Physics·Amir KartonJan M L Martin
Sep 4, 2007·The Journal of Chemical Physics·Dirk Bakowies
Nov 6, 2007·The Journal of Chemical Physics·Dirk Bakowies
Dec 18, 2007·The Journal of Chemical Physics·Thomas B AdlerHans-Joachim Werner
Mar 26, 2008·The Journal of Chemical Physics·Michael E HardingJohn F Stanton
Feb 12, 2009·The Journal of Chemical Physics·Gerald KniziaHans-Joachim Werner
Mar 7, 2009·The Journal of Physical Chemistry. a·Amir KartonJan M L Martin
Aug 3, 2011·The Journal of Chemical Physics·Michael E HardingMihály Kállay
Apr 3, 2012·The Journal of Chemical Physics·Amir Karton, Jan M L Martin
Feb 8, 2013·The Journal of Chemical Physics·Florian PfeifferKirk A Peterson
Sep 14, 2013·The Journal of Chemical Physics·Zoltán RolikMihály Kállay
Nov 27, 2014·The Journal of Physical Chemistry. a·Dirk Bakowies
Nov 18, 2015·Journal of Chemical Theory and Computation·Bun Chan, Leo Radom
Nov 12, 2013·Journal of Chemical Theory and Computation·Bun Chan, Leo Radom
Mar 13, 2012·Journal of Chemical Theory and Computation·Julien BloinoVincenzo Barone
Feb 14, 2012·Journal of Chemical Theory and Computation·Wanyi JiangAngela K Wilson
Jun 10, 2016·The Journal of Chemical Physics·Nitai SylvetskyJan M L Martin
Sep 2, 2016·The Journal of Physical Chemistry. a·J M Simmie, J N Sheahan
May 18, 2017·The Journal of Physical Chemistry. a·Lawrence B HardingStephen J Klippenstein
Aug 2, 2017·The Journal of Physical Chemistry. a·Stephen J KlippensteinBranko Ruscic
Aug 5, 2017·Journal of Chemical Theory and Computation·Ádám GanyeczJózsef Csontos
Oct 22, 2018·The Journal of Chemical Physics·Manoj K KesharwaniJan M L Martin

❮ Previous
Next ❯

Citations

Jul 15, 2021·Journal of Chemical Theory and Computation·Dirk Bakowies, O Anatole von Lilienfeld
Sep 4, 2020·The Journal of Physical Chemistry. a·Karl K Irikura

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.