Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Imaging of transition charge densities involving carbon core excitations by all X-ray sum-frequency generation

Journal Article · · Philosophical Transactions of the Royal Society. A, Mathematical, Physical and Engineering Sciences
 [1];  [2];  [3];  [4];  [5]
  1. Univ. of California, Irvine, CA (United States); Sungkyunkwan Univ., Suwon (Korea); Regents, University of California, Irvine
  2. École Polytechnique Fédérale de Lausanne (Switzerland); Paul Scherrer Inst. (Switzerland)
  3. Stockholm Univ. (Sweden)
  4. Sungkyunkwan Univ., Suwon (Korea)
  5. Univ. of California, Irvine, CA (United States)
+ Show Author Affiliations
X-ray diffraction signals from the time-evolving molecular charge density induced by selective core excitation of chemically inequivalent carbon atoms are calculated. A narrowband X-ray pulse selectively excites the carbon K-edge of the –CH3 or –CH2F groups in fluoroethane (CH3–CH2F). Each excitation creates a distinct core coherence which depends on the character of the electronic transition. Direct propagation of the reduced single-electron density matrix, using real-time time-dependent density functional theory, provides the time-evolving charge density following interactions with external fields. Here, the interplay between partially filled valence molecular orbitals upon core excitation induces characteristic femtosecond charge migration which depends on the core–valence coherence, and is monitored by the sum-frequency generation diffraction signal.
Research Organization:
Univ. of California, Irvine, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
FG02-04ER15571; SC0019484
OSTI ID:
1922841
Alternate ID(s):
OSTI ID: 1609517
Journal Information:
Philosophical Transactions of the Royal Society. A, Mathematical, Physical and Engineering Sciences, Journal Name: Philosophical Transactions of the Royal Society. A, Mathematical, Physical and Engineering Sciences Journal Issue: 2145 Vol. 377; ISSN 1364-503X
Publisher:
The Royal Society PublishingCopyright Statement
Country of Publication:
United States
Language:
English

References (24)

The multi-configurational time-dependent Hartree approach journal January 1990
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal September 2010
Attosecond X-ray Diffraction Triggered by Core or Valence Ionization of a Dipeptide journal December 2017
Real-Time TDDFT Studies of Exciton Decay and Transfer in Silver Nanowire Arrays journal March 2015
Simulation of Near-Edge X-ray Absorption Fine Structure with Time-Dependent Equation-of-Motion Coupled-Cluster Theory journal June 2017
Attosecond Charge Migration with TDDFT: Accurate Dynamics from a Well-Defined Initial State journal August 2017
Phase Cycling RT-TDDFT Simulation Protocol for Nonlinear XUV and X-ray Molecular Spectroscopy journal February 2018
Diffraction-Detected Sum Frequency Generation: Novel Ultrafast X-ray Probe of Molecular Dynamics journal June 2018
Density Matrix Analysis and Simulation of Electronic Excitations in Conjugated and Aggregated Molecules journal September 2002
Modeling Fast Electron Dynamics with Real-Time Time-Dependent Density Functional Theory: Application to Small Molecules and Chromophores journal April 2011
Linear-Response and Real-Time Time-Dependent Density Functional Theory Studies of Core-Level Near-Edge X-Ray Absorption journal August 2012
Comparison of Real-Time and Linear-Response Time-Dependent Density Functional Theories for Molecular Chromophores Ranging from Sparse to High Densities of States journal February 2015
Time-dependent quantum-mechanical methods for molecular dynamics journal April 1988
Visible Light Absorption of N-Doped TiO 2 Rutile Using (LR/RT)-TDDFT and Active Space EOMCCSD Calculations journal October 2011
From charge-transfer to a charge-separated state: a perspective from the real-time TDDFT excitonic dynamics journal January 2014
Propagators for the time-dependent Kohn–Sham equations journal August 2004
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Time-, frequency-, and wavevector-resolved x-ray diffraction from single molecules journal May 2014
Translational and rotational averaging of nonlocal response tensors for nano-shaped light journal January 2018
Time-dependent Hartree-Fock theory of multiphoton ionization: Helium journal September 1987
Time-dependent local-density approximation in real time journal August 1996
Simulating molecular conductance using real-time density functional theory journal October 2006
X-Ray Sum Frequency Diffraction for Direct Imaging of Ultrafast Electron Dynamics journal June 2018
Density-Functional Theory for Time-Dependent Systems journal March 1984

Similar Records

Resonant X-ray Sum-Frequency-Generation Spectroscopy of K-Edges in Acetyl Fluoride
Journal Article · Mon Nov 11 19:00:00 EST 2019 · Journal of Chemical Theory and Computation · OSTI ID:1922847
X-Ray Sum Frequency Diffraction for Direct Imaging of Ultrafast Electron Dynamics
Journal Article · Mon Jun 11 20:00:00 EDT 2018 · Physical Review Letters · OSTI ID:1541326
Resonant X-ray Sum-Frequency-Generation Spectroscopy of K-edges in Acetyl Fluoride
Journal Article · Mon Dec 09 23:00:00 EST 2019 · Journal of Chemcial Theory and Computation · OSTI ID:1580523

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
X-ray diffraction
sum-frequency generation