Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Ultrafast X-Ray Scattering Measurements of Coherent Structural Dynamics on the Ground-State Potential Energy Surface of a Diplatinum Molecule

Journal Article · · Physical Review Letters
 [1];  [2];  [3];  [1];  [1];  [1];  [4];  [3];  [5];  [2];  [6];  [6];  [6];  [7];  [1];  [6];  [1];  [1];  [1]
  1. Technical Univ. of Denmark, Lyngby (Denmark)
  2. Technical Univ. of Denmark, Lyngby (Denmark); Science Inst. of the Univ. of Iceland, Reykjavik (Iceland)
  3. Technical Univ. of Denmark, Lyngby (Denmark); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ., Lund (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Technical Univ. of Denmark, Lyngby (Denmark); Lund Univ., Lund (Sweden)
  6. SLAC National Accelerator Lab. (SLAC), Menlo Park, CA (United States)
  7. SLAC National Accelerator Lab. (SLAC), Menlo Park, CA (United States); Paul Scherrer Inst. (PSI), Villigen (Switzerland)
+ Show Author Affiliations

We present x-ray free electron laser experiments addressing ground-state structural dynamics of the diplatinum anion Pt2POP4 following photoexcitation. The structural dynamics are tracked with < 100 fs time resolution by x-ray scattering, utilizing the anisotropic component to suppress contributions from the bulk solvent. The x-ray data exhibit a strong oscillatory component with period 0.28 ps and decay time 2.2 ps, and structural analysis of the difference signal directly shows this as arising from ground-state dynamics along the PtPt coordinate. Here, these results are compared with multiscale Born-Oppenheimer molecular dynamics simulations and demonstrate how off-resonance excitation can be used to prepare a vibrationally cold excited-state population complemented by a structure-dependent depletion of the ground-state population which subsequently evolves in time, allowing direct tracking of ground-state structural dynamics.

Research Organization:
SLAC National Accelerator Lab. (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1504721
Journal Information:
Physical Review Letters, Journal Name: Physical Review Letters Journal Issue: 6 Vol. 122; ISSN 0031-9007; ISSN PRLTAO
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

References (79)

Resonance Raman intensity analysis investigation of metal-metal bonded transitions: an examination of the1A2u ←1A1g (5dσ* → 6pσ) transition of Pt2(P2O5H2)44− journal November 1999
Coherent anti-Stokes Raman scattering: from proof-of-the-principle experiments to femtosecond CARS and higher order wave-mixing generalizations journal January 2000
Structural Determination of a Photochemically Active Diplatinum Molecule by Time-Resolved EXAFS Spectroscopy journal March 2009
Structural Determination of a Photochemically Active Diplatinum Molecule by Time-Resolved EXAFS Spectroscopy journal March 2009
Disentangling Ultrafast Electronic and Structural Dynamics with X-Ray Lasers journal September 2018
Oriented Ensembles in Ultrafast Electron Diffraction journal June 2006
Femtosecond Stimulated Raman Spectroscopy journal March 2016
Femtosecond Stimulated Raman Spectroscopy journal April 2016
Femtosecond stimulated Raman spectroscopy journal December 2010
Femtosecond pump-probe fluorescence signals from classical trajectories: comparison with wave-packet calculations journal September 2001
Rattle: A “velocity” version of the shake algorithm for molecular dynamics calculations journal October 1983
Electronic structures and photophysics of d 8 -d 8 complexes journal August 2017
Validity of the Bersohn–Zewail model beyond justification journal June 2012
Conservation of vibrational coherence in ultrafast electronic relaxation: The case of diplatinum complexes in solution journal September 2017
Pixel array detector for X-ray free electron laser experiments
  • Philipp, Hugh T.; Hromalik, Marianne; Tate, Mark
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 649, Issue 1 https://doi.org/10.1016/j.nima.2010.11.189
journal September 2011
Photoinduced Structural Dynamics of Molecular Systems Mapped by Time-Resolved X-ray Methods journal May 2017
Introduction: Ultrafast Processes in Chemistry journal August 2017
Spin–Orbit TDDFT Electronic Structure of Diplatinum(II,II) Complexes journal March 2015
Grid-Based Projector Augmented Wave (GPAW) Implementation of Quantum Mechanics/Molecular Mechanics (QM/MM) Electrostatic Embedding and Application to a Solvated Diplatinum Complex journal November 2017
Intersystem Crossing in Diplatinum Complexes journal September 2016
Observing Solvation Dynamics with Simultaneous Femtosecond X-ray Emission Spectroscopy and X-ray Scattering journal February 2016
Solution Structure and Ultrafast Vibrational Relaxation of the PtPOP Complex Revealed by ΔSCF-QM/MM Direct Dynamics Simulations journal February 2018
Chemistry and spectroscopy of binuclear platinum diphosphite complexes journal December 1985
Electronic spectroscopy of d8-d8 diplatinum complexes. 1A2u (d.sigma.* .fwdarw. p.sigma.), 3Eu (dxz,dyz .fwdarw. p.sigma.), and 3,1B2u (d.sigma.* .fwdarw. dx2-y2) excited states of tetrakis(diphosphonato)diplatinate(4-), Pt2(P2O5H2)44- journal April 1987
Bond Shortening (1.4 Å) in the Singlet and Triplet Excited States of [Ir 2 (dimen) 4 ] 2+ in Solution Determined by Time-Resolved X-ray Scattering journal October 2011
Femtosecond Wavepacket Spectroscopy: Influence of Temperature, Wavelength, and Pulse Duration journal March 1995
Energy- and electron-transfer processes of the lowest triplet excited state of tetrakis(diphosphito)diplatinate(II) journal June 1985
UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations journal December 1992
Electronic absorption and emission spectra of binuclear platinum(II) complexes. Characterization of the lowest singlet and triplet excited states of tetrakis(diphosphonato)diplatinate(4-) anion (Pt2(H2P2O5)44-) journal July 1983
Binuclear platinum diphosphite complexes. Crystal structures of tetrapotassium bromotetrakis(diphosphito)diplatinate trihydrate (K4[Pt2(pop)4Br].3H2O), a new linear chain semiconductor, and tetrapotassium dichlorotetrakis(diphosphito)diplatinate dihydrate (K4[Pt2(pop)4Cl2].2H2O) journal July 1983
Quantum and statistical mechanical studies of liquids. 10. Transferable intermolecular potential functions for water, alcohols, and ethers. Application to liquid water journal January 1981
Vibrational Relaxation and Intersystem Crossing of Binuclear Metal Complexes in Solution journal January 2011
Structural Control of 1 A 2u -to- 3 A 2u Intersystem Crossing in Diplatinum(II,II) Complexes journal August 2012
Time-Resolved X-ray Scattering of an Electronically Excited State in Solution. Structure of the 3 A 2u State of Tetrakis-μ-pyrophosphitodiplatinate(II) journal January 2009
Impulsive Control of Ground Surface Dynamics of I 3 - in Solution journal May 2001
Hydrogen Bond Dynamics in Water and Ultrafast Infrared Spectroscopy:  A Theoretical Study journal February 2004
Characterizing the Deformational Isomers of Bimetallic Ir 2 (dimen) 4 2+ (dimen = 1,8-diisocyano- p -menthane) with Vibrational Wavepacket Dynamics journal April 2011
Direct Dynamics Studies of a Binuclear Metal Complex in Solution: The Interplay Between Vibrational Relaxation, Coherence, and Solvent Effects journal June 2014
Coherent structural trapping through wave packet dispersion during photoinduced spin state switching journal May 2017
Achieving few-femtosecond time-sorting at hard X-ray free-electron lasers journal February 2013
Tuning the activities of cuprous oxide nanostructures via the oxide-metal interaction journal May 2020
Introducing a standard method for experimental determination of the solvent response in laser pump, X-ray probe time-resolved wide-angle X-ray scattering experiments on systems in solution journal January 2013
Disentangling detector data in XFEL studies of temporally resolved solution state chemistry journal January 2015
Tracking the picosecond deactivation dynamics of a photoexcited iron carbene complex by time-resolved X-ray scattering journal January 2018
Assessing computationally efficient isomerization dynamics: ΔSCF density-functional theory study of azobenzene molecular switching journal December 2011
Comparison of simple potential functions for simulating liquid water journal July 1983
Impulsive excitation of coherent vibrational motion ground surface dynamics induced by intense short pulses journal November 1994
Simulation of ultrafast dynamics and pump–probe spectroscopy using classical trajectories journal May 1996
Role of electronic localization in the phosphorescence of iridium sensitizing dyes journal October 2012
Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion journal February 2016
Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution journal June 2018
Anisotropy in the preparation of symmetric top excited states. I. One-photon electric dipole excitation journal March 1999
On the calculation of x-ray scattering signals from pairwise radial distribution functions journal November 2015
Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method journal June 2010
The atomic simulation environment—a Python library for working with atoms journal June 2017
On the interpretation of time-resolved anisotropic diffraction patterns journal November 2010
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
Imaging of the umbrella motion and tunneling in ammonia molecules by strong-field ionization journal October 2016
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Real-space grid implementation of the projector augmented wave method journal January 2005
Δ self-consistent field method to obtain potential energy surfaces of excited molecules on surfaces journal August 2008
Localized atomic basis set in the projector augmented wave method journal November 2009
Strong-Field Induced Vibrational Coherence in the Ground Electronic State of Hot I 2 journal March 2008
Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated [ Co ( terpy ) 2 ] 2 + journal June 2016
Formation of Ground-State Vibrational Wave Packets in Intense Ultrashort Laser Pulses journal September 2006
Quantum-Phase Resolved Mapping of Ground-State Vibrational D 2 Wave Packets via Selective Depletion in Intense Laser Pulses journal September 2006
Linac Coherent Light Source: The first five years journal March 2016
Excited-state structure by time-resolved X-ray diffraction journal February 2002
Analysis of time-resolved X-ray scattering data from solution-state systems journal February 2010
The X-ray Pump–Probe instrument at the Linac Coherent Light Source journal April 2015
Anisotropy enhanced X-ray scattering from solvated transition metal complexes journal February 2018
An object-oriented scripting interface to a legacy electronic structure code journal January 2002
Excited-state Structure of a Platinum Complex by X-ray Analysis journal November 2002
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density text January 1988
Fundamental Limits on Spatial Resolution in Ultrafast X-ray Diffraction journal May 2017
Delta Self-Consistent Field as a method to obtain potential energy surfaces of excited molecules on surfaces text January 2008
Localized atomic basis set in the projector augmented wave method text January 2013
Imaging of the umbrella motion and tunneling in the ammonia molecule by strong-field ionization text January 2016
Anisotropy enhanced X-ray scattering from solvated transition metal complexes text January 2018

Cited By (15)

Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal January 2020
Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy journal January 2019
A versatile experimental system for tracking ultrafast chemical reactions with X-ray free-electron lasers journal September 2019
Solvent-dependent complex reaction pathways of bromoform revealed by time-resolved X-ray solution scattering and X-ray transient absorption spectroscopy journal November 2019
Ultrafast structural dynamics of photo-reactions observed by time-resolved x-ray cross-correlation analysis text January 2019
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal January 2020
Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy journal January 2019
The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems journal May 2008
Ultrafast structural dynamics of photo-reactions observed by time-resolved x-ray cross-correlation analysis journal March 2019
Theory of ultrafast x-ray scattering by molecules in the gas phase journal November 2019
A versatile experimental system for tracking ultrafast chemical reactions with X-ray free-electron lasers journal September 2019
Simulation of ultrafast excited-state dynamics and elastic x-ray scattering by quantum wavepacket dynamics journal September 2019
Solvent-dependent complex reaction pathways of bromoform revealed by time-resolved X-ray solution scattering and X-ray transient absorption spectroscopy journal November 2019
Ultrafast structural dynamics of photo-reactions observed by time-resolved x-ray cross-correlation analysis text January 2019
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering text January 2020

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS