TY - JOUR
T1 - Hydrogen Abstraction Reactions from Phenolic Compounds by Peroxyl Radicals
T2 - Multireference Character and Density Functional Theory Rate Constants
AU - Galano, Annia
AU - Muñoz-Rugeles, Leonardo
AU - Alvarez-Idaboy, Juan Raul
AU - Bao, Junwei Lucas
AU - Truhlar, Donald G.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2016/7/14
Y1 - 2016/7/14
N2 - An assessment of multireference character in transition states is considered to be an important component in establishing the expected reliability of various electronic structure methods. In the present work, the multireference characters of the transition states and the forming and breaking of bonds for a large set of hydrogen abstraction reactions from phenolic compounds by peroxyl radicals have been analyzed using the T1, M, B1, and GB1 diagnostics. The extent of multireference character depends on the system and on the conditions under which the reaction takes place, and some systematic trends are observed. In particular, the multireference character is found to be reduced by solvation, the size of the phenolic compound, and deprotonation in aqueous solution. However, the deviations of calculated rate constants from experimental ones are not correlated with the extent of multireference character. The performance of single-determinant density functional theory was investigated for the kinetics of these reactions by comparing calculated rate constants to experimental data; the results from these analyses showed that the M05 functional performs well for the task at hand.
AB - An assessment of multireference character in transition states is considered to be an important component in establishing the expected reliability of various electronic structure methods. In the present work, the multireference characters of the transition states and the forming and breaking of bonds for a large set of hydrogen abstraction reactions from phenolic compounds by peroxyl radicals have been analyzed using the T1, M, B1, and GB1 diagnostics. The extent of multireference character depends on the system and on the conditions under which the reaction takes place, and some systematic trends are observed. In particular, the multireference character is found to be reduced by solvation, the size of the phenolic compound, and deprotonation in aqueous solution. However, the deviations of calculated rate constants from experimental ones are not correlated with the extent of multireference character. The performance of single-determinant density functional theory was investigated for the kinetics of these reactions by comparing calculated rate constants to experimental data; the results from these analyses showed that the M05 functional performs well for the task at hand.
UR - http://www.scopus.com/inward/record.url?scp=84978761402&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84978761402&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.5b07662
DO - 10.1021/acs.jpca.5b07662
M3 - Article
C2 - 26378461
AN - SCOPUS:84978761402
SN - 1089-5639
VL - 120
SP - 4634
EP - 4642
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 27
ER -