scholarly journals Publisher’s Note: “Charge-transfer selectivity and quantum interference in real-time electron dynamics: Gaining insights from time-dependent configuration interaction simulations” [J. Chem. Phys. 152, 194111 (2020)]

2020 ◽  
Vol 152 (24) ◽  
pp. 249902
Author(s):  
Raghunathan Ramakrishnan
Keyword(s):  
Charge Transfer ◽  
Real Time ◽  
Configuration Interaction ◽  
Quantum Interference ◽  
Chem Phys ◽  
Time Dependent ◽  
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>

scholarly journals Correction: Analysis and visualization of energy densities. I. Insights from real-time time-dependent density functional theory simulations

2021 ◽  
Author(s):  
Junjie Yang ◽  
Zheng Pei ◽  
Jingheng Deng ◽  
Yuezhi Mao ◽  
Qin Wu ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Real Time ◽  
Density Functional ◽  
Chem Phys ◽  
Time Dependent ◽  
Functional Theory ◽  
Phys Chem Chem Phys ◽  
Dependent Density

Correction for ‘Analysis and visualization of energy densities. I. Insights from real-time time-dependent density functional theory simulations’ by Junjie Yang et al., Phys. Chem. Chem. Phys., 2020, 22, 26838–26851, DOI: 10.1039/d0cp04206d.

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

2020 ◽  
Author(s):  
Raghunathan Ramakrishnan
Keyword(s):  
Electron Transfer ◽  
Configuration Interaction ◽  
Quantum Interference ◽  
Quantum Coherence ◽  
Gold Atom ◽  
Electron Injection ◽  
Time Dependent ◽  
Destructive Interference ◽  
Donor States ◽  
Meta Isomer

Many-electron wavepacket dynamics based on time-dependent configuration interaction (TDCI) is a numerically rigorous approach to quantitatively model electron-transfer across molecular junctions. TDCI simulations of cyanobenzene thiolates---para- and meta-linked to an acceptor gold atom---show donor states conjugating with the benzene $\pi$-network to allow better through-molecule electron migration in the para isomer compared to the meta counterpart. For dynamics involving non-conjugating states, we find electron-injection to stem exclusively from distance-dependent non-resonant quantum mechanical tunneling, in which case the meta isomer exhibits better dynamics. Computed trend in donor-to-acceptor net-electron transfer through differently linked azulene bridges agrees with the trend seen in low-bias conductivity measurements. Disruption of $\pi$-conjugation has been shown to be the cause of diminished electron-injection through the 1,3-azulene, a pathological case for graph-based diagnosis of destructive quantum interference. Furthermore, we demonstrate quantum interference of many-electron wavefunctions 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 benzene, $\sigma$ and $\pi$ MOs localized at the donor terminal are in-phase leading to constructive interference of electron density distribution while phase-flip of one of the MOs in the meta isomer results in destructive interference. These findings suggest that a priori detection of orbital phase-flip and quantum coherence conditions can aid in molecular device design strategies.

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