Laser-induced electron dynamics including photoionization: A heuristic model within time-dependent configuration interaction theory

2009 ◽  
Vol 131 (11) ◽  
pp. 114304 ◽  
Author(s):  
Stefan Klinkusch ◽  
Peter Saalfrank ◽  
Tillmann Klamroth
Keyword(s):  
Configuration Interaction ◽  
Time Dependent ◽  
Heuristic Model ◽  
Interaction Theory ◽  
Electron Dynamics

scholarly journals Quantum Interference in Real-Time Electron-Dynamics: Gaining Insights from Time-Dependent Configuration Interaction Simulations

2019 ◽  
Author(s):  
Raghunathan Ramakrishnan
Keyword(s):  
Configuration Interaction ◽  
Quantum Interference ◽  
Quantum Coherence ◽  
Gold Atom ◽  
Electron Injection ◽  
Time Dependent ◽  
Destructive Interference ◽  
Electron Dynamics ◽  
Initial State ◽  
Donor States

<p>Femtosecond electron dynamics based on time-dependent configuration interaction (TDCI) is a numerically rigorous approach for quantitative modeling of electron-injection across molecular junctions. Our simulations of cyanobenzene thiolates---para- and meta-linked to an acceptor gold atom---corroborate aromatic resonance stabilization effects and show donor states \emph{conjugating} with the benzene $\pi$-network to exhibit superior electron-injection dynamics across the para-linked isomer compared to the meta counterpart. For a \emph{non-conjugating} initial state, we find electron-injection through the meta-channel to stem from non-resonant quantum mechanical tunneling. Furthermore, we demonstrate quantum interference to drive para- vs. meta- selectivity in the coherent evolution of superposed $\pi$(CN)- and $\sigma$(NC-C)-type wavepackets. Analyses reveal that in the para-linked molecule, $\sigma$, and $\pi$ MOs localized at the donor terminal are \emph{in-phase} leading to constructive interference of electron density distribution while phase-flip of one of the MOs in the meta-linked molecule results in destructive interference. The findings reported here suggest that \emph{a priori} detection of orbital phase-flip and quantum coherence conditions can aid in molecular device design strategies.</p><p></p>

Quantum Interference in Real-Time Electron-Dynamics: Gaining Insights from Time-Dependent Configuration Interaction Simulations

2019 ◽  
Author(s):  
Raghunathan Ramakrishnan
Keyword(s):  
Configuration Interaction ◽  
Quantum Interference ◽  
Quantum Coherence ◽  
Gold Atom ◽  
Electron Injection ◽  
Time Dependent ◽  
Destructive Interference ◽  
Electron Dynamics ◽  
Initial State ◽  
Donor States

<p> p.p1 {margin: 0.0px 0.0px 0.0px 0.0px; font: 11.0px Menlo; color: #000000; background-color: #ffffc9} span.s1 {font-variant-ligatures: no-common-ligatures} span.s2 {font-variant-ligatures: no-common-ligatures; color: #2cb11b} span.s3 {font-variant-ligatures: no-common-ligatures; color: #c611c6} span.s4 {font-variant-ligatures: no-common-ligatures; color: #be631a} </p><p><b>Femtosecond electron dynamics based on time-dependent configuration interaction (TDCI) is a numerically rigorous approach for quantitative modeling of electron-injection </b><b>across molecular junctions.</b></p> <p><b>Our simulations of cyanobenzene thiolates---para- and meta-linked to an acceptor </b><b>gold atom---corroborate aromatic resonance stabilization effects and show donor states </b><b>\emph</b><b>{</b><b>conjugating</b><b>}</b><b> with the benzene </b><b>$</b><b>\pi</b><b>$</b><b>-network to exhibit superior electron-injection dynamics across the para-linked isomer compared to the meta counterpart. For a </b><b>\emph</b><b>{</b><b>non-conjugating</b><b>}</b><b> initial state, we find electron-injection through the meta-channel to stem from non-resonant </b><b>quantum mechanical tunneling. </b><b>Furthermore, we demonstrate quantum interference to drive para- vs. meta- selectivity in the coherent evolution of superposed </b><b>$</b><b>\pi</b><b>$</b><b>(CN)- and </b><b>$</b><b>\sigma</b><b>$</b><b>(NC-C)-type wavepackets. </b><b>Analyses reveal that in the para-linked molecule, </b><b>$</b><b>\sigma</b><b>$</b><b>, and </b><b>$</b><b>\pi</b><b>$</b><b> MOs localized at the donor terminal are </b><b>\emph</b><b>{</b><b>in-phase</b><b>}</b><b> leading to constructive interference of electron density distribution while phase-flip of one of the MOs in the meta-linked molecule results in destructive interference. </b><b>The findings reported here suggest that </b><b>\emph</b><b>{</b><b>a priori</b><b>}</b><b> detection of orbital phase-flip and quantum coherence conditions can aid in molecular device design strategies.</b></p><p></p>

Electron dynamics across molecular wires: A time-dependent configuration interaction study

2013 ◽  
Vol 420 ◽  
pp. 44-49 ◽  
Author(s):  
Raghunathan Ramakrishnan ◽  
Shampa Raghunathan ◽  
Mathias Nest
Keyword(s):  
Configuration Interaction ◽  
Molecular Wires ◽  
Time Dependent ◽  
Electron Dynamics ◽  
Interaction Study
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