Title: Determining Orientations of Optical Transition Dipole Moments Using Ultrafast X-ray Scattering

Journal Article · · Journal of Physical Chemistry Letters
ORCiD logo [1];  [2];  [1];  [1];  [2];  [3];  [3];  [3];  [3];  [3];  [1];  [1];  [1];  [3]; ORCiD logo [4]; ORCiD logo [5];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Brown Univ., Providence, RI (United States)
  2. Univ. of Edinburgh, Edinburgh (United Kingdom)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Univ. of Copenhagen, Copenhagen (Denmark)
  5. Univ. of Copenhagen, Copenhagen (Denmark); King Fahd Univ. of Petroleum & Minerals, Dhahran (Saudi Arabia)
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Here, identification of the initially prepared, optically active state remains a challenging problem in many studies of ultrafast photoinduced processes. We show that the initially excited electronic state can be determined using the anisotropic component of ultrafast time-resolved X-ray scattering signals. The concept is demonstrated using the time-dependent X-ray scattering of N-methyl morpholine in the gas phase upon excitation by a 200 nm linearly polarized optical pulse. Analysis of the angular dependence of the scattering signal near time zero renders the orientation of the transition dipole moment in the molecular frame and identifies the initially excited state as the 3pz Rydberg state, thus bypassing the need for further experimental studies to determine the starting point of the photoinduced dynamics and clarifying inconsistent computational results.

Research Organization:
Brown Univ., Providence, RI (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-76SF00515; SC0017995
OSTI ID:
1490811
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 22 Vol. 9; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (39)

Elements of Modern X-ray Physics book March 2011
Optical Preparation of Aligned Reagents journal May 1982
Ultrafast Electron Diffraction: Oriented Molecular Structures in Space and Time journal November 2005
Oriented Ensembles in Ultrafast Electron Diffraction journal June 2006
Gas-phase electron diffraction from laser-aligned molecules journal August 2015
Observation of Structural Wavepacket Motion: The Umbrella Mode in Rydberg-Excited N -Methyl Morpholine journal July 2017
Photodissociation of Simple Molecules in the Gas Phase journal September 2001
Ultrafast Electron Diffraction. 4. Molecular Structures and Coherent Dynamics journal March 1994
Failure of Time-Dependent Density Functional Theory for Long-Range Charge-Transfer Excited States:  The Zincbacteriochlorin−Bacteriochlorin and Bacteriochlorophyll−Spheroidene Complexes journal March 2004
Molecular Structure and Orientation:  Concepts from Femtosecond Dynamics journal April 2001
Ultrafast X-ray and Electron Diffraction:  Theoretical Considerations journal November 1997
Ultrafast X-ray Diffraction Theory journal November 1998
Qualitatively Incorrect Features in the TDDFT Spectrum of Thiophene-Based Compounds journal December 2014
Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction journal March 2016
Diffractive imaging of a rotational wavepacket in nitrogen molecules with femtosecond megaelectronvolt electron pulses journal April 2016
Imaging of alignment and structural changes of carbon disulfide molecules using ultrafast electron diffraction journal September 2015
First lasing and operation of an ångstrom-wavelength free-electron laser journal August 2010
Toward structural femtosecond chemical dynamics: imaging chemistry in space and time journal January 2014
Coherence in nonradiative transitions: internal conversion in Rydberg-excited N-methyl and N-ethyl morpholine journal January 2017
Photodissociation of molecular beams of aryl halides journal December 1974
Photodissociation of molecular beams of aryl halides: Translational energy distribution of the fragments journal March 1977
Extraction of the transition dipole matrix from the photodissociation of oriented/aligned parent molecules journal December 1996
Quantification of transition dipole strengths using 1D and 2D spectroscopy for the identification of molecular structures via exciton delocalization: Application to α-helices journal November 2012
Self-interaction corrected density functional calculations of molecular Rydberg states journal November 2013
Reconstruction of three-dimensional molecular structure from diffraction of laser-aligned molecules journal July 2014
Applications of linear Dichroism Spectroscopy journal January 1978
On the interpretation of time-resolved anisotropic diffraction patterns journal November 2010
Time-Resolved Electron Diffraction from Selectively Aligned Molecules journal May 2009
X-Ray Diffraction from Isolated and Strongly Aligned Gas-Phase Molecules with a Free-Electron Laser journal February 2014
Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction journal June 2015
Self-Referenced Coherent Diffraction X-Ray Movie of Ångstrom- and Femtosecond-Scale Atomic Motion journal October 2016
International Tables for Crystallography book January 2006
X-ray detectors at the Linac Coherent Light Source journal April 2015
Doppler line shape of atomic fluorescence excited by molecular photodissociation journal January 1963
Directional Dynamics in the Photodissociation of Oriented Molecules journal March 2004
Determination of transition dipole moments from time-resolved photoelectron spectroscopy journal July 2003
Imaging Techniques for the Study of Chemical Reaction Dynamics journal October 1995
P HOTOELECTRON A NGULAR D ISTRIBUTIONS journal October 2003
Determining the orientation of transition moments and depolarization by fluorescence polarizing angle spectrum journal January 2015

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