TY - JOUR

T1 - N-H and N-Cl Homolytic Bond Dissociation Energies and Radical Stabilization Energies: An Assessment of Theoretical Procedures Through Comparison With Benchmark-Quality W2w Data

AU - O’Reilly, R.J.

AU - Karton, Amir

AU - Radom, L.

PY - 2012/4/15

Y1 - 2012/4/15

N2 - The performance of a large variety of contemporary density functional theory (DFT), double-hybrid DFT, and high-level Gaussian-n (Gn) procedures has been evaluated for the calculation of bond dissociation energies (BDEs) and radical stabilization energies (RSEs) associated with N[BOND]X bonds (X = H, Cl). The chosen set of 62 N[BOND]X systems (31 N[BOND]H and 31 N[BOND]Cl) span a wide range of biologically relevant species. As reference values, we used benchmark-quality W2w data that we recently obtained as part of a systematic thermochemical study of substituent effects in these systems. Of the Gn schemes, the modified G4 procedures (G4-5H and G4(MP2)-6X) perform somewhat better than the corresponding standard G4 procedures for the N[BOND]X BDEs of these systems. For the N[BOND]H RSEs, G3X, G3X(MP2), G3X(MP2)-RAD, G4-5H, and G4(MP2)-6X emerge as excellent performers, with mean absolute deviations (MADs) from the benchmark W2w values of 0.9–1.4 kJ mol–1. However, for the N[BOND]Cl RSEs, G4 is the best performer, with an MAD of 1.7 kJ mol–1. The BDEs of both N[BOND]H and N[BOND]Cl bonds represent a challenge for DFT procedures. In particular, only a handful of functionals (namely, B3P86, M05-2X, M06-2X, and ROB2-PLYP) perform well, with MADs ≤ 4.5 kJ mol−1 for both bond types. Nearly all of the considered DFT procedures perform significantly better for the computation of RSEs, due to a significantly larger degree of error cancelation compared with the BDEs. For the RSEs, BH&HLYP, M05-2X, M06, M06-2X, BMK, PBE0, B2-PLYP, B2GP-PLYP, B2T-PLYP, and ROB2-PLYP are the best performers, with MADs ≤ 4.2 kJ mol−1. Reliable values of N[BOND]H and N[BOND]Cl BDEs may be obtained by using the RSEs calculated by these functionals in conjunction with a thermochemical cycle involving an experimental (or high-level theoretical) BDE for the H2N[BOND]H or H2N[BOND]Cl bond. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011

AB - The performance of a large variety of contemporary density functional theory (DFT), double-hybrid DFT, and high-level Gaussian-n (Gn) procedures has been evaluated for the calculation of bond dissociation energies (BDEs) and radical stabilization energies (RSEs) associated with N[BOND]X bonds (X = H, Cl). The chosen set of 62 N[BOND]X systems (31 N[BOND]H and 31 N[BOND]Cl) span a wide range of biologically relevant species. As reference values, we used benchmark-quality W2w data that we recently obtained as part of a systematic thermochemical study of substituent effects in these systems. Of the Gn schemes, the modified G4 procedures (G4-5H and G4(MP2)-6X) perform somewhat better than the corresponding standard G4 procedures for the N[BOND]X BDEs of these systems. For the N[BOND]H RSEs, G3X, G3X(MP2), G3X(MP2)-RAD, G4-5H, and G4(MP2)-6X emerge as excellent performers, with mean absolute deviations (MADs) from the benchmark W2w values of 0.9–1.4 kJ mol–1. However, for the N[BOND]Cl RSEs, G4 is the best performer, with an MAD of 1.7 kJ mol–1. The BDEs of both N[BOND]H and N[BOND]Cl bonds represent a challenge for DFT procedures. In particular, only a handful of functionals (namely, B3P86, M05-2X, M06-2X, and ROB2-PLYP) perform well, with MADs ≤ 4.5 kJ mol−1 for both bond types. Nearly all of the considered DFT procedures perform significantly better for the computation of RSEs, due to a significantly larger degree of error cancelation compared with the BDEs. For the RSEs, BH&HLYP, M05-2X, M06, M06-2X, BMK, PBE0, B2-PLYP, B2GP-PLYP, B2T-PLYP, and ROB2-PLYP are the best performers, with MADs ≤ 4.2 kJ mol−1. Reliable values of N[BOND]H and N[BOND]Cl BDEs may be obtained by using the RSEs calculated by these functionals in conjunction with a thermochemical cycle involving an experimental (or high-level theoretical) BDE for the H2N[BOND]H or H2N[BOND]Cl bond. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011

U2 - 10.1002/qua.23210

DO - 10.1002/qua.23210

M3 - Article

VL - 112

SP - 1862

EP - 1878

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 8

ER -