RT Journal Article
T1 Substituent effects on nonadiabatic excited state dynamics: Inertial, steric, and electronic effects in methylated butadienes
A1 MacDonell, Ryan
A1 Corrales Castellanos, María Eugenia
A1 Boguslavskiy, Andrey
A1 Bañares Morcillo, Luis
A1 Stolow, Albert
A1 Schuurman, Michael
AB The photochemical dynamics of double-bond-containing hydrocarbons is exemplified by the smallest alkenes, ethylene and butadiene. Chemical substituents can alter both decay timescales and photoproducts through a combination of inertial effects due to substituent mass, steric effects due to substituent size, and electronic (or potential) effects due to perturbative changes to the electronic potential energy surface. Here, we demonstrate the interplay of different substituent effects on 1,3-butadiene and its methylated derivatives using a combination of ab initio simulation of nonadiabatic dynamics and time-resolved photoelectron spectroscopy. The purely inertial effects of methyl substitution are simulated through the use of mass 15 “heavy-hydrogen” atoms. As expected from both inertial and electronic influences, the excited-state dynamics is dominated by pyramidalization at the unsubstituted carbon sites. Although the electronic effects of methyl group substitution are weak, they alter both decay timescales and branching ratios by influencing the initial path taken by the excited wavepacket following photoexcitation.
SN 0021-9606
YR 2020
FD 2020
LK https://hdl.handle.net/20.500.14352/94630
UL https://hdl.handle.net/20.500.14352/94630
LA eng
NO Ryan J. MacDonell, María E. Corrales, Andrey E. Boguslavskiy, Luis Bañares, Albert Stolow, Michael S. Schuurman; Substituent effects on nonadiabatic excited state dynamics: Inertial, steric, and electronic effects in methylated butadienes. J. Chem. Phys. 28 February 2020; 152 (8): 084308. https://doi.org/10.1063/1.5139446
NO Natural Sciences and Engineering Research Council of Canada
NO Ministerio de Cultura (España)
DS Docta Complutense
RD 7 abr 2025