Title: Strong-field- versus weak-field-ionization pump-probe spectroscopy

Journal Article · · Physical Review A
 [1];  [2];  [3];  [4];  [5];  [3];  [2]
  1. Stony Brook Univ., NY (United States); DOE/OSTI
  2. Stony Brook Univ., NY (United States)
  3. Temple Univ., Philadelphia, PA (United States)
  4. Univ. of Vienna, Wien (Austria)
  5. Hungarian Academy of Sciences, Budapest (Hungary)
+ Show Author Affiliations

Ionization can serve as a universal probe of excited-state dynamics in molecules, such as internal conversion, dissociation, and isomerization. These processes are of fundamental importance to a wide array of dynamics in biology, chemistry, and physics. In recent years, there has been significant debate about the relative merits of strong-field ionization (SFI), which involves multiphoton absorption, versus weak-field ionization (WFI), where a single photon is absorbed, as probes of these dynamics. SFI is advantageous because it uses wavelengths that are relatively easy to generate, and one can always ionize the molecule with sufficient intensity. However, for SFI it is difficult to calculate observables, such as the time-dependent ion yield, since the calculation of the ionization dynamics including multiphoton processes is computationally expensive and difficult to carry out for many molecular geometries. WFI has the advantage that calculations of observables are tractable. However, the generation and implementation of the appropriate wavelengths (photon energies) can be challenging, and the fixed energy of the probe can lead to technical complications in following the dynamics from excited states back down to the ground state. Here we present a quantitative comparison of the two approaches for following the excited-state dynamics of two molecules, diiodomethane and uracil. The combination of internal conversion and dissociation in these molecules provides an ideal comparison of WFI and SFI as a probe. We compare the measurements with calculations of the dynamics. Furthermore, our work indicates that while SFI and WFI provide qualitatively similar information about the excited-state dynamics, only WFI results can be compared quantitatively with present-day calculations.

Research Organization:
State Univ. of New York (SUNY), Albany, NY (United States); Temple Univ., Philadelphia, PA (United States)
Sponsoring Organization:
National Science Foundation; USDOE Office of Science (SC)
Grant/Contract Number:
FG02-08ER15983; FG02-08ER15984
OSTI ID:
1609962
Journal Information:
Physical Review A, Journal Name: Physical Review A Journal Issue: 5 Vol. 98; ISSN PLRAAN; ISSN 2469-9926
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

References (76)

Time-Resolved Photoelectron Spectroscopy of Nonadiabatic Dynamics in Polyatomic Molecules book March 2008
Femtosecond Time-Resolved Photoelectron Spectroscopy journal June 2004
Spin-Orbit Ab Initio Investigation of the Ultraviolet Photolysis of Diiodomethane journal April 2007
Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8 journal November 2015
Newton-X: a surface-hopping program for nonadiabatic molecular dynamics: Newton-X
  • Barbatti, Mario; Ruckenbauer, Matthias; Plasser, Felix
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1 https://doi.org/10.1002/wcms.1158
journal June 2013
Nonadiabatic dynamics: The SHARC approach
  • Mai, Sebastian; Marquetand, Philipp; González, Leticia
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 6 https://doi.org/10.1002/wcms.1370
journal May 2018
Columbus-a program system for advanced multireference theory calculations: The Columbus multireference program system
  • Lischka, Hans; Müller, Thomas; Szalay, Péter G.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 2 https://doi.org/10.1002/wcms.25
journal January 2011
Relativistic Douglas-Kroll-Hess theory: Relativistic DKH theory journal June 2011
Ultrafast transient absorption spectroscopy: principles and application to photosynthetic systems journal July 2009
Stabilization energy and positional effects in halogen-substituted alkyl ions journal December 1988
30.4 nm He (II) photoelectron spectra of organic molecules Part VI. Halogeno-compounds (C, H, X; X = Cl, Br, I) journal January 1982
Solvation effects on the iodoform ultraviolet direct photodissociation reaction: opening the photoisomerization channel journal June 2000
The restricted active space (RAS) state interaction approach with spin–orbit coupling journal May 2002
Multiconfiguration perturbation theory with imaginary level shift journal August 1997
Conical intersections, pseudorotation and coherent oscillations in ultrafast photodissociation of group-6 metal hexacarbonyls journal September 2000
Photoion mass spectrometry of adenine, thymine and uracil in the 6–22eV photon energy range journal July 2005
Singlet excited state dynamics of uracil and thymine derivatives: A femtosecond fluorescence upconversion study in acetonitrile journal October 2006
The on-the-fly surface-hopping program system Newton-X: Application to ab initio simulation of the nonadiabatic photodynamics of benchmark systems journal August 2007
Comprehensive data analysis of femtosecond transient absorption spectra: A review journal March 2012
Efficient and Flexible Computation of Many-Electron Wave Function Overlaps journal February 2016
Intersystem Crossing Pathways in the Noncanonical Nucleobase 2-Thiouracil: A Time-Dependent Picture journal May 2016
Femtosecond Time-Resolved Photoelectron Spectroscopy journal April 2004
Non-Born-Oppenheimer Liouville-von Neumann Dynamics. Evolution of a Subsystem Controlled by Linear and Population-Driven Decay of Mixing with Decoherent and Coherent Switching journal May 2005
SHARC: ab Initio Molecular Dynamics with Surface Hopping in the Adiabatic Representation Including Arbitrary Couplings journal March 2011
Ultrafast Electron Diffraction. 5. Experimental Time Resolution and Applications journal March 1994
Photoelectron-photoion coincidence study of the ionization and fragment appearance potentials of bromo- and iodomethanes journal March 1975
Ultrafast Internal Conversion of Electronically Excited RNA and DNA Nucleosides in Water journal September 2000
Intrinsic Lifetimes of the Excited State of DNA and RNA Bases journal November 2002
Singlet Excited-State Behavior of Uracil and Thymine in Aqueous Solution:  A Combined Experimental and Computational Study of 11 Uracil Derivatives journal January 2006
Ab Initio Molecular Dynamics and Time-Resolved Photoelectron Spectroscopy of Electronically Excited Uracil and Thymine journal August 2007
Nonadiabatic Dynamics of Uracil: Population Split among Different Decay Mechanisms journal June 2011
Ultrafast Relaxation Dynamics of Uracil Probed via Strong Field Dissociative Ionization journal November 2013
Photoinduced Nonadiabatic Dynamics of Pyrimidine Nucleobases: On-the-Fly Surface-Hopping Study with Semiempirical Methods journal March 2009
Femtosecond Dynamics and Vibrational Coherence in Gas-Phase Ultraviolet Photodecomposition of Cr(CO) 6 journal June 1998
Ultrafast X-ray Diffraction Theory journal November 1998
Monitoring Nonadiabatic Dynamics of the RNA Base Uracil by UV Pump–IR Probe Spectroscopy journal May 2013
Clocking transient chemical changes by ultrafast electron diffraction journal March 1997
Discerning vibronic molecular dynamics using time-resolved photoelectron spectroscopy journal September 1999
Revealing Deactivation Pathways Hidden in Time-Resolved Photoelectron Spectra journal October 2016
Ultrafast intersystem crossing dynamics in uracil unravelled by ab initio molecular dynamics journal January 2014
Near-UV photodissociation dynamics of CH 2 I 2 journal January 2016
The IPEA dilemma in CASPT2 journal January 2017
High-level multireference methods in the quantum-chemistry program system COLUMBUS: Analytic MR-CISD and MR-AQCC gradients and MR-AQCC-LRT for excited states, GUGA spin–orbit CI and parallel CI density journal January 2001
Electronic relaxation dynamics in DNA and RNA bases studied by time-resolved photoelectron spectroscopy journal January 2004
Direct semiclassical simulation of photochemical processes with semiempirical wave functions journal June 2001
Photodissociation of diiodomethane in acetonitrile solution and fragment recombination into iso-diiodomethane studied with ab initio molecular dynamics simulations journal August 2004
Ultrafast excited-state dynamics in photochromic N -salicylideneaniline studied by femtosecond time-resolved REMPI spectroscopy journal November 2004
Excited states dynamics of DNA and RNA bases: Characterization of a stepwise deactivation pathway in the gas phase journal February 2005
Critical appraisal of the fewest switches algorithm for surface hopping journal April 2007
Dyson orbitals for ionization from the ground and electronically excited states within equation-of-motion coupled-cluster formalism: Theory, implementation, and examples journal December 2007
Photodissociation of molecular beams of methylene iodide and iodoform journal July 1975
CH 2 I 2 photodissociation: Dynamical modeling journal September 1988
Ultrafast internal conversion and photodissociation of molecules excited by femtosecond 155 nm laser pulses journal October 1999
Excited state dynamics in SO 2 . I. Bound state relaxation studied by time-resolved photoelectron-photoion coincidence spectroscopy journal May 2014
Electronic state spectroscopy of diiodomethane (CH 2 I 2 ): Experimental and computational studies in the 30 000–95 000 cm −1 region journal May 2014
Mega-electron-volt ultrafast electron diffraction at SLAC National Accelerator Laboratory journal July 2015
Ultrafast internal conversion dynamics of highly excited pyrrole studied with VUV/UV pump probe spectroscopy journal February 2017
Relaxation mechanisms of UV-photoexcited DNA and RNA nucleobases journal November 2010
Femtosecond dynamics of DNA-mediated electron transfer journal May 1999
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
Structures and Electron Attachment Properties of Halomethanes ( CX n Y m , X = H, F; Y = Cl, Br, I; n = 0,4; m = 4 n ) journal February 2001
Photoelectron Spectra of the Halides of Elements in Groups III, IV, V and VI
  • Potts, A. W.; Lempka, H. J.; Streets, D. G.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 268, Issue 1184 https://doi.org/10.1098/rsta.1970.0061
journal November 1970
Dyson norms in XUV and strong-field ionization of polyatomics: Cytosine and uracil journal November 2012
Understanding the modulation mechanism in resonance-enhanced multiphoton probing of molecular dynamics journal March 2015
Nonadiabatic dynamics and multiphoton resonances in strong-field molecular ionization with few-cycle laser pulses journal May 2016
Time-resolved measurement of internal conversion dynamics in strong-field molecular ionization journal August 2017
Time-Resolved Electron Diffraction from Selectively Aligned Molecules journal May 2009
Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction journal June 2015
Strong Field Molecular Ionization in the Impulsive Limit: Freezing Vibrations with Short Pulses journal February 2016
Diffractive Imaging of Coherent Nuclear Motion in Isolated Molecules journal October 2016
Following Ultrafast Radiationless Relaxation Dynamics With Strong Field Dissociative Ionization: A Comparison Between Adenine, Uracil, and Cytosine journal January 2012
XSEDE: Accelerating Scientific Discovery journal September 2014
Watching a Protein as it Functions with 150-ps Time-Resolved X-ray Crystallography journal June 2003
Thymine Dimerization in DNA Is an Ultrafast Photoreaction journal February 2007
Imaging Atomic Structure and Dynamics with Ultrafast X-ray Scattering journal June 2007
Nonadiabatic dynamics and multiphoton resonances in strong field molecular ionization with few cycle laser pulses text January 2016

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Computing the Ultrafast and Radiationless Electronic Excited State Decay of Cytosine and 5‐methyl‐cytosine Cations: Uncovering the Role of Dynamic Electron Correlation journal May 2019

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