000180500 001__ 180500
000180500 005__ 20190316235446.0
000180500 0247_ $$2doi$$a10.1063/1.4738878
000180500 022__ $$a0021-9606
000180500 02470 $$2ISI$$a000312491400017
000180500 037__ $$aARTICLE
000180500 245__ $$aEvaluation of the importance of spin-orbit couplings in the nonadiabatic quantum dynamics with quantum fidelity and with its efficient “on-the-fly” ab initio semiclassical approximation
000180500 260__ $$bAmerican Institute of Physics$$c2012$$aMelville
000180500 269__ $$a2012
000180500 300__ $$a8
000180500 336__ $$aJournal Articles
000180500 520__ $$aWe propose to measure the importance of spin-orbit couplings (SOCs) in the nonadiabatic molecular quantum dynamics rigorously with quantum fidelity. To make the criterion practical, quantum fidelity is estimated efficiently with the multiple-surface dephasing representation (MSDR). The MSDR is a semiclassical method that includes nuclear quantum effects through interference of mixed quantumclassical trajectories without the need for the Hessian of potential energy surfaces. Two variants of the MSDR are studied, in which the nuclei are propagated either with the fewest-switches surface hopping or with the locally mean field dynamics. The fidelity criterion and MSDR are first tested on one-dimensional model systems amenable to numerically exact quantum dynamics. Then, the MSDR is combined with “on-the-fly” computed electronic structure to measure the importance of SOCs and nonadiabatic couplings in the photoisomerization dynamics of CH2NH 2 considering 20 electronic states and in the collision of F + H2 considering six electronic states.
000180500 6531_ $$aspin-orbit couplings
000180500 6531_ $$anonadiabatic quantum dynamics
000180500 6531_ $$aquantum fidelity
000180500 6531_ $$a“on-the-fly” ab initio semiclassical approximation
000180500 700__ $$0242994$$g187721$$aZimmermann, Tomas
000180500 700__ $$aVanicek, Jiri$$g181577$$0240352
000180500 773__ $$j137$$tJournal of Chemical Physics$$q22A516
000180500 8564_ $$uhttp://jcp.aip.org/resource/1/jcpsa6/v137/i22/p22A516_s1$$zURL
000180500 8564_ $$uhttps://infoscience.epfl.ch/record/180500/files/JChemPhys_137_22A516.pdf$$zPublisher's version$$s1140418$$yPublisher's version
000180500 909C0 $$xU11812$$0252116$$pLCPT
000180500 909CO $$ooai:infoscience.tind.io:180500$$qGLOBAL_SET$$pSB$$particle
000180500 917Z8 $$x221270
000180500 917Z8 $$x263863
000180500 937__ $$aEPFL-ARTICLE-180500
000180500 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000180500 980__ $$aARTICLE