A Standard Set of Pericyclic Reactions of Hydrocarbons for the Benchmarking of Computational Methods:  The Performance of ab Initio, Density Functional, CASSCF, CASPT2, and CBS-QB3 Methods for the Prediction of Activation Barriers, Reaction Energetics, and Transition State Geometries

Güner, V.; Khuong, Kelli S.; Leach, Andrew G.; Lee, Patrick S.; Bartberger, Michael D.; Houk, K. N.

doi:10.1021/jp035501w

Cited by 347 publications

(332 citation statements)

References 103 publications

Supporting

Mentioning

300

Contrasting

Unclassified

Order By: Relevance

“…[42,43] CBS-QB3 has been extensively tested in several benchmarks and is expected to produce reliable results. [42,43,[45][46][47] The mean absolute deviation in the G2 test set is reported to be 0.87 kcal mol À1 . [42] The accuracy in predicting kinetics of pericyclic reactions is most important to our study.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Kinetic Stability and Propellant Performance of Green Energetic Materials

Rahm

Brinck

2010

Chemistry A European J

View full text Add to dashboard Cite

Outside contact: Cells in multicellular organisms regulate their adhesion through specialized integrin receptors, which relay signals bidirectionally between the inside and outside of cells. The transmembrane domains (see picture, blue; the integrin–talin complex is red and green) of integrins are the center of the signaling process. Recently, structures of these domains have been reported that shed light on the signal transduction mechanism.

show abstract

Section: Methodsmentioning

confidence: 99%

“…[42] The accuracy in predicting kinetics of pericyclic reactions is most important to our study. Guner et al evaluated this for 11 different reactions [46,47] and CBS-QB3 was found to have a mean absolute deviation value of 1.9 and a standard deviation of 1.6 kcal mol À1 , when compared to experimentally determined activation enthalpies.…”

Section: Methodsmentioning

confidence: 99%

Kinetic Stability and Propellant Performance of Green Energetic Materials

Rahm

Brinck

2010

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…A wide variety of properties, including structures (12), thermochemistry (11) (including activation barriers; ref. 65), spectroscopic quantities of various types (13,66), and responses to external perturbations (67), can be computed effectively. As discussed above, SCRF methods (or simply ignoring the solvent entirely, an approximation that is sometimes acceptable, particularly in nonpolar solvents or when a quantity that is insensitive to the dielectric of the environment is being computed) enable a relatively straightforward extension of gas-phase quantum chemical methods to obtaining results for molecules in solution.…”

Section: Applicationsmentioning

confidence: 99%

Ab initioquantum chemistry: Methodology and applications

Friesner

2005

Proc. Natl. Acad. Sci. U.S.A.

297

228

View full text Add to dashboard Cite

This Perspective provides an overview of state-of-the-art ab initio quantum chemical methodology and applications. The methods that are discussed include coupled cluster theory, localized second-order Moller-Plesset perturbation theory, multireference perturbation approaches, and density functional theory. The accuracy of each approach for key chemical properties is summarized, and the computational performance is analyzed, emphasizing significant advances in algorithms and implementation over the past decade. Incorporation of a condensed-phase environment by means of mixed quantum mechanical͞molecular mechanics or self-consistent reaction field techniques, is presented. A wide range of illustrative applications, focusing on materials science and biology, are discussed briefly.coupled cluster ͉ density functional theory ͉ second-order Modler-Plesser perturbation theory ͉ mixed quantum͞molecular mechanics O ver the past three decades, ab initio quantum chemistry has become an essential tool in the study of atoms and molecules and, increasingly, in modeling complex systems such as those arising in biology and materials science. The underlying core technology is computational solution of the electronic Schrodinger equation; given the positions of a collection of atomic nuclei, and the total number of electrons in the system, calculate the electronic energy, electron density, and other properties by means of a well defined, automated approximation (a ''model chemistry''). The ability to obtain ''goodenough'' solutions to the electronic Schrodinger equation for systems containing tens, or even hundreds, of atoms has revolutionized the ability of theoretical chemistry to address important problems in a wide range of disciplines; the Nobel Prize awarded to John Pople and Walter Kohn in 1998 is a reflection of this observation.In its exact form, the electronic Schrodinger equation is a many-body problem, whose computational complexity grows exponentially with the number of electrons, and hence, a brute force solution is intractable. Hartree-Fock theory, a mean field approach, produces reasonable results for many properties but is incapable of providing a robust description of reactive chemical events in which electron correlation has a major role. Thus, a key problem has been the development of treatments of electron correlation that exhibit a tractable scaling in computational effort with the size of the system. The considerable progress that has been made along these lines is outlined below.Given a well defined theoretical framework of approximation, the next requirement is efficient computational implementation. Considerable sophistication is required to achieve acceptable accuracy and efficiency; the leading quantum chemistry programs are millions of lines of computer code, and mathematical algorithms to reduce formal scaling of computational effort with system size have an increasingly crucial role in meeting the challenge of handling complex system relevant to practical applications. Below, the most important comp...

show abstract

“…Small molecules in the gas phase are typically addressed by high-level methods such as CCSD(T), QCISD(T) and MRCI, which in many cases are as accurate as experiments (Friesner, 2005). A wide variety of properties such as: structures (Thomas, 1993); thermochemistry (Guner, 2003); spectroscopic quantities (Stanton & Bartlett (1993);and kinetics (Fernandez-Ramos, 2006) can be effectively computed.…”

Section: Theoretical Methodologymentioning

confidence: 99%