A dataset of highly accurate homolytic NBr bond dissociation energies obtained by Means of W2 theory

O'Reilly, Robert J.; Karton, Amir

doi:10.1002/qua.25024

Cited by 31 publications

(14 citation statements)

References 133 publications

(167 reference statements)

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“…By way of contrast, the worst performance is obtained in the case of BH&HLYP (MAD = 43.1 kJ mol −1 ). The notably poor performance of BH&HLYP for the computation of BDEs have been reported previously, for example, in the case of NX (X = H, Cl, and Br) bonds . The double‐hybrid DFT methods offer MADs ranging from 2.6 (PWPB95‐D3) to 14.2 (B2‐PLYP) kJ mol −1 .…”

Section: Resultsmentioning

confidence: 89%

Stability of the chlorinated derivatives of the DNA/RNA nucleobases, purine and pyrimidine toward radical formation via homolytic CCl bond dissociation

Kaliyeva

Zhumagali

Akhmetova

et al. 2016

Int J of Quantum Chemistry

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The chlorinated derivatives of nucleobases (and nucleosides), as well as those of purine, have well‐established anticancer activity, and in some cases, are also shown to be involved in the link between chronic inflammatory conditions and the development of cancer. In this investigation, the stability of all of the isomeric forms of the chlorinated nucleobases, purine and pyrimidine are investigated from the perspective of their homolytic CCl bond dissociation energies (BDEs). The products of these reactions, namely chlorine atom and the corresponding carbon‐centered radicals, may be of importance in terms of potentiating biological damage. Initially, the performance of a wide range of contemporary theoretical procedures were evaluated for their ability to afford accurate CCl BDEs, using a recently reported set of 28 highly accurate CCl BDEs obtained by means of W1w theory. Subsequent to this analysis, the G3X(MP2)‐RAD procedure (which achieves a mean absolute deviation of merely 1.3 kJ mol−1, with a maximum deviation of 5.0 kJ mol−1) was employed to obtain accurate gas‐phase homolytic CCl bond dissociation energies for a wide range of chlorinated isomers of the DNA/RNA nucleobases, purine and pyrimidine.

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Section: Resultsmentioning

confidence: 89%

Stability of the chlorinated derivatives of the DNA/RNA nucleobases, purine and pyrimidine toward radical formation via homolytic CCl bond dissociation

Kaliyeva

Zhumagali

Akhmetova

et al. 2016

Int J of Quantum Chemistry

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“…In contrast, BLYP exhibits the worst performance of any of the functionals considered in the present study, with an MAD of 36.8 kJ mol -1 . It is of interest to note that the BLYP functional has also shown relatively poor performance for the computation of C-Cl BDEs [70] (MAD = 30.9 kJ mol -1 ), N-H and N-Cl BDEs (MADs = 23.7 and 25.2 kJ mol -1 , respectively) [71] and N-Br BDEs (MAD = 27.1 kJ mol -1 ) [72]. The LD of BLYP, amounting to 44.8 kJ mol -1 is associated with the computation of the BDE of (NH2)(BH2)BCl.…”

Section: Mongolian Journal Of Chemistrymentioning

confidence: 99%

Homolytic B–Cl bond dissociation energies of chloroborane-type molecules

Li¹,

O'Reilly²

2022

Mong. J. Chem.

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This study reports accurate gas-phase homolytic B–Cl bond dissociation energies, obtained using the benchmark-quality W1w thermochemical protocol, for a set of 25 chloroborane-type molecules (known herein as the BCl25BDE dataset). The BDEs of these species differ by as much as 136.5 kJ mol-1 at 298 K, with (BH2)2BCl having the lowest BDE (388.5 kJ mol-1 at 298 K) and (CH3)HBCl having the highest (525.1 kJ mol-1 ). Using the W1w BDEs as reference values, the accuracy of a diverse set of more economical DFT procedures (which may be applied to the study of molecules sufficiently large that the use of benchmark-quality methods such as W1w is rendered computationally prohibitive) have been investigated. As a result of this analysis, the most accurate methods for the computation of B–Cl BDEs are ωB97/A'VQZ (MAD = 3.0 kJ mol-1 ) and M06/A'VTZ (MAD = 3.2 kJ mol-1 ). The double-hybrid functional DSD-PBEP86 in conjunction with the A'VQZ basis set (MAD = 4.0 kJ mol-1 ) was found to give the lowest largest deviation (LD = 6.4 kJ mol-1 ) of any of methods considered in this assessment study.

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“…For more details of all the subsets of every database, as well as references to their original sources, and a better overview of their overlaps, see also the Supporting Information …”

Section: Structure Of the Databasementioning

confidence: 99%

ACCDB: A collection of chemistry databases for broad computational purposes

Morgante

Peverati

2018

J Comput Chem

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The importance of databases of reliable and accurate data in chemistry has substantially increased in the past two decades. Their main usage is to parametrize electronic structure theory methods, and to assess their capabilities and accuracy for a broad set of chemical problems. The collection we present here—ACCDB—includes data from 16 different research groups, for a total of 44,931 unique reference data points, all at a level of theory significantly higher than density functional theory, and covering most of the periodic table. It is composed of five databases taken from literature (GMTKN, MGCDB84, Minnesota2015, DP284, and W4‐17), two newly developed reaction energy databases (W4‐17‐RE and MN‐RE), and a new collection of databases containing transition metals. A set of expandable software tools for its manipulation is also presented here for the first time, as well as a case study where ACCDB is used for benchmarking commercial CPUs for chemistry calculations. © 2018 Wiley Periodicals, Inc.

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A dataset of highly accurate homolytic NBr bond dissociation energies obtained by Means of W2 theory

Cited by 31 publications

References 133 publications

Stability of the chlorinated derivatives of the DNA/RNA nucleobases, purine and pyrimidine toward radical formation via homolytic CCl bond dissociation

Stability of the chlorinated derivatives of the DNA/RNA nucleobases, purine and pyrimidine toward radical formation via homolytic CCl bond dissociation

Homolytic B–Cl bond dissociation energies of chloroborane-type molecules

ACCDB: A collection of chemistry databases for broad computational purposes

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