Related Experiment Video
Updated: Aug 4, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
A quantum wave-packet study of intersystem crossing effects in the O(3P2,1,0,1D2)+H2 reaction
Tian-Shu Chu1, Xin Zhang, Ke-Li Han
1State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Abstract:
We present for the first time an exact quantum study of spin-orbit-induced intersystem crossing effects in the title reaction. The time-dependent wave-packet method, combined with an extended split operator scheme, is used to calculate the fine-structure resolved cross section. The calculation involves four electronic potential-energy surfaces of the 1A' state [J. Dobbyn and P. J. Knowles, Faraday Discuss. 110, 247 (1998)], the 3A' and the two degenerate 3A" states [S. Rogers, D. Wang, A. Kuppermann, and S. Wald, J. Phys. Chem. A 104, 2308 (2000)], and the spin-orbit couplings between them [B. Maiti, and G. C. Schatz, J. Chem. Phys. 119, 12360 (2003)]. Our quantum dynamics calculations clearly demonstrate that the spin-orbit coupling between the triplet states of different symmetries has the greatest contribution to the intersystem crossing, whereas the singlet-triplet coupling is not an important effect. A branch ratio of the spin state Pi32 to Pi12 of the product OH was calculated to be approximately 2.75, with collision energy higher than 0.6 eV, when the wave packet was initially on the triplet surfaces. The quantum calculation agrees quantitatively with the previous quasiclassical trajectory surface hopping study.
Related Concept Videos
Energy Diagrams, Transition States, and Intermediates
¹H NMR: Interpreting Distorted and Overlapping Signals
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are slanted or...
π Electron Effects on Chemical Shift: Overview
UV–Vis Spectroscopy: Molecular Electronic Transitions
Atomic Absorption Spectroscopy: Interference
Spectral interference occurs when signals from other elements or molecules overlap with the analyte signal, falsely elevating or masking the analyte's absorbance. This interference can be corrected using Zeeman,...
Atomic Emission Spectroscopy: Interference

